PULP COMPOSITION

Abstract

 A novel pulp composition having oil resistance and/or water resistance is provided by a pulp composition comprising a liquid-repellent compound and a pulp substrate, wherein the liquid-repellent compound is a compound having a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and is not a fatty acid ester having a glycoside bond, and the pulp substrate comprises bagasse pulp.

Description

Technical Field

[0001] The present disclosure relates to a pulp composition, and in particular to a pulp composition having oil resistance and/or water resistance.

Background Art

[0002] Patent Literature 1 discloses that a composition containing sugar fatty acid ester and hemicellulose or lignin can be used to modify the barrier function of cellulose-based materials.

[0003] In the composition disclosed in Patent Literature 1, sugar fatty acid ester is an essential ingredient, and the use of other ingredients in place of sugar fatty acid ester has not been considered. Furthermore, Patent Literature 1 does not disclose that the composition exhibits excellent oil resistance and water resistance.

Citation List

Patent Literature

[0004]  Patent Literature 1: WO 2021/019468

Summary of Invention

Technical Problem

[0005] An object of the present disclosure is to provide a novel pulp composition having oil resistance and/or water resistance.

Solution to Problem

[0006] The present disclosure includes the following embodiments.

[Item 1]

[0007] A pulp composition comprising a liquid-repellent compound and a pulp substrate, wherein

the liquid-repellent compound is a compound having a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and is not a fatty acid ester having a glycoside bond, and

the pulp substrate comprises bagasse pulp.

[Item 2]

[0008] The pulp composition according to item 1, wherein the liquid-repellent compound has at least one group selected from the group consisting of:

        -OC(=O)R, -COOR, -NHCOR and -CONHR,

wherein R is each independently a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.

[Item 3]

[0009] The pulp composition according to item 1 or 2, wherein the liquid-repellent compound is a compound formed by modifying amine, polyol or polycarboxylic acid with a hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.

[Item 4]

[0010] The pulp composition according to any one of items 1 to 3, wherein an amount of the liquid-repellent compound is 0.5% by weight or more and 25% by weight or less based on the pulp substrate.

[Item 5]

[0011] The pulp composition according to any one of items 1 to 4, wherein an amount of the bagasse pulp is 20% by weight or more and 100% by weight or less in the pulp substrate.

[Item 6]

[0012] The pulp composition according to any one of items 1 to 5, wherein the pulp composition comprises a dispersant.

[Item 7]

[0013] The pulp composition according to any one of items 1 to 6, wherein the pulp composition comprises a combination chemical for paper.

[Item 8]

[0014] The pulp composition according to any one of items 1 to 7, wherein the pulp composition comprises a sizing agent.

[Item 9]

[0015] The pulp composition according to any one of items 1 to 8, wherein the pulp composition comprises aluminum sulfate.

[Item 10]

[0016] A pulp formed article formed from the pulp composition according to any one of items 1 to 9.

[Item 11]

[0017] The pulp formed article according to item 10, which is for food contact.

[Item 12]

[0018] A method for producing a pulp composition, comprising treating a pulp substrate with a repellent comprising a liquid repellent compound, wherein

the liquid-repellent compound is a compound having a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and is not a fatty acid ester having a glycoside bond, and

the pulp substrate comprises bagasse pulp.

[Item 13]

[0019] The method for producing a pulp composition according to item 12, wherein the liquid-repellent compound has at least one group selected from the group consisting of:

        -OC(=O)R, -COOR, -NHCOR and -CONHR,

wherein R is each independently a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.

Advantageous Effect of Invention

[0020] The pulp composition of the present disclosure has excellent oil resistance and/or water resistance.

Description of Embodiments

<Definition of Terms>

[0021] As used herein, the "n valent group" refers to a group having n bonds, i.e., a group forming n bonds. The "n valent organic group" refers to a n valent group containing carbon. Such organic groups are not limited, but can be hydrocarbon groups or derivatives thereof. The derivative of the hydrocarbon group refers to a group that has one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, halogen and the like at the end or in the molecular chain of a hydrocarbon group.

[0022] As used herein, the "hydrocarbon group" refers to a group containing carbon and hydrogen and a group in which a hydrogen atom is removed from the hydrocarbon. Such hydrocarbon groups are not limited, but include C_1-20 hydrocarbon groups, such as an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The above "aliphatic hydrocarbon group" may be either linear, branched, or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may include one or more ring structures. In an explicit term, the hydrocarbon group may be substituted by one or more substituents.

[0023] Whether or not the phrases "independently at each occurrence", "independently with each other", "each independently" or similar expressions are explicitly described herein, unless otherwise described that they are exceptions, when a plurality of terms (symbols) that can occur in a chemical structure is defined, such definition is applied independently to each occurrence.

[0024] The chemical structures described herein should be understood not to encompass chemical structures that are recognized by those skilled in the art as being chemically impossible or extremely unstable.

<Pulp composition>

[0025] The pulp composition of the present disclosure comprises a liquid-repellent compound and a pulp substrate. The pulp composition of the present disclosure has excellent oil resistance and/or water resistance, preferably both of the two.

[0026] The pulp composition of the present disclosure is obtained by adding a liquid-repellent compound to a pulp substrate. The pulp composition may also be obtained by treating a pulp substrate with a repellent containing a liquid-repellent compound. In that case the amount of the repellent added and the composition of the repellent may be adjusted so that the respective components are in desired amounts. The components in the repellent may also be separately added to the pulp composition as an additive.

[0027] The pulp composition of the present disclosure may not have any one selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom. The pulp composition of the present disclosure can impart liquid-repellency to a substrate without including these fluorine-containing compounds.

[0028] The pulp composition may have a pH of 3 to 10, for example, 5 to 9, and in particular 6 to 8. The amount of the respective components may be adjusted to achieve such pH.

{Pulp substrate}

[0029] The pulp composition comprises a pulp substrate. The pulp substrate is composed of pulp, which may be wood pulp, non-wood pulp, wastepaper pulp or the like, including at least bagasse pulp.

[Wood pulp]

[0030] Wood pulp includes softwood kraft pulp from the genus Abies, Pinus and the like, and hardwood kraft pulp from the genus Acacia, Eucalyptus, Fagus, and Populus (e.g., poplar). Softwood kraft pulp includes, for example, unbleached softwood kraft pulp (NUKP), bleached softwood pulp (NBKP), semi-bleached softwood kraft pulp (NSBKP), and softwood sulfite pulp. Examples of hardwood kraft pulp include unbleached hardwood kraft pulp (LUKP), bleached hardwood kraft pulp (LBKP), semi-bleached hardwood kraft pulp (LSBKP), and hardwood sulfite pulp. The pulp may be used singly or in combination. Other than kraft pulp, in addition to softwood kraft pulp and hardwood kraft pulp, wood pulp includes stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), thermo-ground pulp (TGP), chemi-ground pulp (CGP), crushed wood pulp (GP), thermomechanical pulp (TMP), and other mechanical pulps. Furthermore, wastepaper pulp includes a disintegrated wastepaper pulp, a disintegrated and deinked wastepaper pulp or a disintegrated, deinked and bleached wastepaper pulp produced from brown waste paper, kraft envelope wastepaper, wastepaper of magazines, wastepaper of newspapers, wastepaper of flyers, sorted office paper, wastepaper of cardboard, hard white wastepaper, Kent wastepaper, wastepaper of poster paper and bond paper.

[Non-wood pulp]

[0031] Examples of non-wood pulp include pulp prepared from bagass, kenaf, bamboo, linter, cotton, linen, hemp, ramie, straw, esparto, Manila hemp, Xyzal hemp, yellow hemp, flax, ganpi, paper bush and kozo (Japanese paper mulberry).

[Fiber length of pulp]

[0032] The pulp has an average fiber length of preferably 0.1 mm or more, more preferably 0.3 mm or more and further preferably 0.5 mm or more from the viewpoint of the improvement in oil resistance, and preferably 5.0 mm or less, more preferably 4.0 mm or less, further preferably 3.0 mm or less, particularly preferably 2.0 mm or less, and most preferably 1.2 mm or less from the viewpoint of ease of manufacture.

[Fiber width of pulp]

[0033] From the viewpoint of the improvement in oil resistance, the pulp has an average fiber width of preferably 5 µm or more, more preferably 10 µm or more, and further preferably 15 µmm or more, and preferably 50 µm or less, more preferably 40 µm or less, and further preferably 30 µm or less.

[Composition of pulp substrate]

[0034] The amount of bagasse pulp may be more than 0% by weight, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and is preferably 20% by weight or more, and may be 100% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less, and is for example, 80% by weight or less in the pulp substrate.

[0035] The total amount of pulp other than bagasse may be 0% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 99% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less in the pulp substrate.

[0036] The amount of wood pulp may be 0% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, or 70% by weight or more, and may be 99% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, or 10% by weight or less in the pulp substrate.

[Form of pulp substrate]

[0037] The form of the pulp substrate when the liquid-repellent compound is added thereto may be, for example, pulp alone, pulp slurry, or a pulp product. Specific examples thereof include pulp, such as bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp; bleached or unbleached high-yield pulp such as groundwood pulp, mechanical pulp, or thermomechanical pulp; pulp slurry including the above pulp; and a pulp product such as paper, a paper container and a pulp formed article.

[Amount of pulp substrate]

[0038] The amount of pulp substrate may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, or 90% by weight or more, and may be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less in the pulp composition. Typically, when the pulp composition is prepared by internal addition, the amount of pulp substrate is 30% by weight or less in the pulp composition; when the pulp composition is prepared by external addition, the amount of pulp substrate may be 75% by weight or more in the pulp composition.

[0039] The amount of the pulp substrate may be 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, or 99% by weight or more, and may be 99.9% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 75% by weight or less, 65% by weight or less, or 55% by weight or less in the pulp composition excluding liquid medium.

{Liquid medium}

[0040] The pulp composition may comprise a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The liquid medium is typically an aqueous medium, and in particular, water. The liquid medium may comprise a liquid medium derived from repellent.

[Amount of liquid medium]

[0041] The amount of the liquid medium may be 0.1% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more, 75% by weight or more, 90% by weight or more, or 95% by weight or more, and may be 99% by weight or less, 75% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 4% by weight or less, or 3% by weight or less in the pulp composition. Typically, when the pulp composition is prepared by internal addition, the amount of the liquid medium is 50% by weight or more, and in particular 90% by weight or more in the pulp composition; when the pulp composition is prepared by external addition, the amount of the liquid medium is 30% by weight or less, and in particular, 10% by weight or less in the pulp composition.

{Liquid-repellent compound}

[0042] The pulp composition includes a liquid-repellent compound. Details of the types of the liquid-repellent compound are the same as those of the liquid-repellent compound in <Repellent>.

[Amount of liquid-repellent compound]

[0043] The amount of the liquid-repellent compound may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and is preferably 0.5% by weight or more, and may be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is for example 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less based on the pulp substrate.

[0044]  The amount of the liquid repellent compound which is a modified body of amine may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and is preferably 0.5% by weight or more, and may be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is for example 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less based on the pulp substrate.

[0045] The amount of the liquid repellent compound which is a modified body of polyol may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and is preferably 0.5% by weight or more, and may be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is for example 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less based on the pulp substrate.

[0046] The amount of the liquid repellent compound which is a modified body of polycarboxylic acid may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and is preferably 0.5% by weight or more, and may be 25% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is for example 15% by weight or less, 5.0% by weight or less, or 3.0% by weight or less based on the pulp substrate.

[0047] The surface of the pulp substrate (for example, a pulp product such as paper, a paper container and a pulp formed article) may be externally treated with the liquid-repellent compound. The amount of the liquid-repellent compound included in the coating layer formed by the external addition treatment may be 0.01 g/m² or more, 0.03 g/m² or more, 0.05 g/m² or more, 0.1 g/m² or more, 0.3 g/m² or more, 0.5 g/m² or more, or 1.0 g/m² or more, and may be 5.0 g/m² or less, 4.0 g/m² or less, 3.0 g/m² or less, 2.0 g/m² or less, 1.0 g/m² or less, 0.5 g/m² or less, 0.3 g/m² or less, or 0.1 g/m² or less.

{Dispersant}

[0048] The pulp composition may comprise a dispersant. Details of the types of the dispersant are the same as those of the dispersant in <Repellent>.

[Amount of dispersant]

[0049] The amount of the dispersant may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is preferably 5.0% by weight or less, and more preferably 3.0% by weight or less based on the pulp substrate.

{Paper strength agent}

[0050] The pulp composition may comprise a paper strength agent. Examples of paper strength agents include:

a polyacrylamide-based paper strength agent such as cationic polyacrylamide, anionic polyacrylamide and amphoteric polyacrylamide;

a polysaccharide-based paper strength agent such as starch, enzyme modified starch, thermochemically modified starch, oxidized starch, esterified starch, etherified starch (e.g., hydroxyethylated starch), aldehyde starch, cationized starch, starch, xanthan gum, gum karaya, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, cellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, chitin nanofiber, cellulose nanofiber and pullulan, and a modified polysaccharide thereof (e.g., a modified polysaccharide prepared by introducing a hydroxyl group or a cationic group thereinto);

a polyamide-based paper strength agent such as polyamide resin, polyamine resin, polyamide-polyamine resin, polyamide-epichlorohydrin resin, polyamide-polyamine-epichlorohydrin resin, polyamide-polyurea-formaldehyde resin and epoxidized polyamide resin;

a urea/melamine paper strength agent such as urea resin, melamine resin, urea-formaldehyde resin and melamine-formaldehyde resin;

a polyvinyl alcohol paper strength agent such as polyvinyl alcohol, completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxyl modified polyvinyl alcohol, silanol modified polyvinyl alcohol, cation modified polyvinyl alcohol and terminal alkyl modified polyvinyl alcohol; and

a styrene butadiene copolymer, polyvinyl acetate, a vinyl chloride-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, polyacrylic ester, fatty acid diamide, polyethyleneimine resin and ketone aldehyde resin.

[0051] A polyacrylamide-based paper strength agent, a polysaccharide-based paper strength agent and a polyamide-based paper strength agent are preferred as the paper strength agent in the present disclosure.

[Amount of paper strength agent]

[0052] The amount of the paper strength agent may be 0.1% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less, and is preferably 5.0% by weight or less based on the pulp.

{Sizing agent}

[0053] The pulp composition may comprise a sizing agent. Examples of sizing agents include a cationic sizing agent, an anionic sizing agent, a neutral sizing agent and an amphoteric sizing agent, a rosin-based sizing agent (for example, an acidic rosin-based sizing agent and a neutral rosin-based sizing agent), alkyl ketene dimer and alkenyl succinic anhydride.

[Amount of sizing agent]

[0054] The amount of the sizing agent may be 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.75% by weight or more, 1.0% by weight or more, 2.0% by weight or more, or 3.0% by weight or more, and may be 10% by weight or less, 7.5% by weight or less, 5.0% by weight or less, 4.0% by weight or less, 3.0% by weight or less, 2.0% by weight or less, 1.0% by weight or less, 0.75% by weight or less, or 0.5% by weight or less based on the pulp.

{Other additives}

[0055] The pulp composition may also include another additive used for producing a pulp product in addition to the above components, including a combination chemical for paper such as a fixing agent (e.g., aluminum sulfate), a coagulant and an agglomerating agent (e.g., polyamine-based resin), an yield improver (e.g., polyacrylamide-based resin), an organic acid (e.g., formic acid, acetic acid), a dye, a slime control agent, and an antifoaming agent.

[Amount of other additives]

[0056] The amount of other additives may be 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, and may be 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 3% by weight or less, or 1% by weight or less, respectively, based on the pulp substrate.

<Repellent>

[0057] The repellent in present disclosure adheres to a substrate (in particular, a pulp substrate) and imparts liquid-repellency, for example, water resistance, oil resistance, water-repellency, oil-repellency and/or antifouling properties to the substrate, and may function as a water-resistant agent, an oil-resistant agent, a water-repellent agent, an oil-repellent agent and/or an antifouling agent.

[0058] The repellent in the present disclosure includes a liquid-repellent compound as the active ingredient. The liquid repellent compound itself may be used as a repellent, or may be combined with other components described below and used as a repellent.

[0059] The repellent of the present disclosure may not include one selected from the group consisting of a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group having 4 or more carbon atoms, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group and a compound having a fluorine atom. The repellent of the present disclosure can impart liquid-repellency to a substrate without these fluorine compounds.

[0060] The volume abundance ratio of particles with a size of 100 µm or larger in the repellent of the present disclosure may be 0.1% or more, 0.3% or more, 0.5% or more, 1% or more, 1.5% or more, 3% or more, 4% or more, 5% or more, or 10% or more, and may be 50% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, 3% or less, or 1.5% or less, as measured by laser diffraction scattering. The method for setting the volume abundance ratio of particles with a size of 1 µm or larger as measured by laser diffraction scattering to the above range is not limited, and for example, particles in the raw material and/or dispersion may be formed into fine particles using a pulverizer or a homogenizer.

[0061] The repellent in the present disclosure may have a volume median diameter as measured by laser diffraction scattering of 0.01 µm or more, 0.05 µm or more, 0.1 µm or more, 0.2 µm or more, 0.3 µm or more, 0.4 µm or more, 0.5 µm or more, 0.6 µm or more, 1.0 µm or more, 5.0 µm or more, 10.0 µm or more, 20.0 µm or more, 30.0 µm or more, 40.0 µm or more, 50.0 µm or more, 75.0 µm or more, or 100.0 µm or more, and 100 µm or less, 90 µm or less, 80 µm or less, 70 µm or less, 60 µm or less, 50 µm or less, 40 µm or less, 30 µm or less, 20 µm or less, 10 µm or less, 5 µm or less, 3 µm or less, 1 µm or less, 0.9 µm or less, 0.8 µm or less, 0.7 µm or less, 0.6 µm or less, 0.5 µm or less, 0.4 µm or less, 0.3 µm or less, or 0.2 µm or less, and is preferably 1 µm or less. In the present disclosure, the volume median diameter refers to the median diameter (D50) in a volume-based particle size distribution by laser diffraction scattering.

[0062] The particle obtained by removing liquid medium from repellent (e.g., an oil resistant agent for pulp) which is the water-dispersible composition in the present disclosure by air dry at room temperature may have an average particle size obtained from an observation image by a scanning electron microscope of 0.01 µm or more, 0.05 µm or more, 0.1 µm or more, 0.2 µm or more, 0.3 µm or more, 0.4 µm or more, 0.5 µm or more, or 0.6 µm or more, and 10 µm or less, 5 µm or less, 3 µm or less, 1 µm or less, 0.9 µm or less, 0.8 µm or less, 0.7 µm or less, 0.6 µm or less, 0.5 µm or less, 0.4 µm or less, 0.3 um or less, or 0.2 µm or less, and is preferably 1 µm or less. To set the particle size to the above range, for example, particles in the raw material and/or dispersion may be formed into fine particles using a pulverizer or a homogenizer. The room temperature means 20°C to 30°C, in particular 25°C.

[0063] The repellent in the present disclosure may have an ionic charge density of -1,000 µeq/g or more, -800 peq/g or more, -600 µeq/g or more, -500 µeq/g or more, -400 µeq/g or more, -250 µeq/g or more, -100 µeq/g or more, - 50 µeq/g or more, -25 µeq/g or more, 0 µeq/g or more, 1 µeq/g or more, 25 µeq/g or more, 50 µeq/g or more, 100 µeq/g or more, 200 µeq/g or more, and is preferably -600 µeq/g or more, and may be, for example, -400 µeq/g or more, -200 µeq/g or more, -50 µeq/g or more, and 5,000 µeq/g or less, 2,500 µeq/g or less, 1,000 µeq/g or less, 750 µeq/g or less, 500 µeq/g or less, 400 µeq/g or less, 350 µeq/g or less, 300 µeq/g or less, 200 µeq/g or less, 100 µeq/g or less, or 50 µeq/g or less, and is preferably 1,000 µeq/g or less, more preferably 500 µeq/g or less, and for example, 300 µeq/g or less. In particular, it is preferable that the repellent in the present disclosure has an ionic charge density of -600 µeq/g or more and 100 µeq/g or less. The ionic charge density of the repellent in the present disclosure may be measured by, for example, the following method.

[0064] The anion requirement of a sample solution having a solid content of 0.1 g/L is measured by a particle charge meter (MUTEK PCD-06 manufactured by BTG) using a 1/1,000 N potassium polyvinylsulfonate solution to calculate the ionic charge density (cationic charge density) by the following equation (1). Alternatively, the cation requirement is measured in the same manner by using poly(diallyldimethylammonium chloride) solution instead of the potassium polyvinylsulfonate solution to calculate the ionic charge density (anionic charge density) by the following equation (1).

A: cation requirement or anion requirement (µeq/L)

B: Concentration of sample solution (g/L)

{Liquid repellent compound}

[0065] The liquid repellent compound in the present disclosure adheres to a substrate (in particular, a pulp substrate) and imparts liquid repellency such as water resistance, oil resistance, water-repellency, oil-repellency and/or antifouling properties to the substrate.

[Characteristics]

[0066] The possible characteristics of the liquid repellent compound will be described below.

[0067] The liquid repellent compound may have a HD (n-hexadecane) contact angle of 10° or more, 20° or more, 25° or more, 30° or more, 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 60° or more, or 65° or more, and is preferably 25° or more, more preferably 30° or more, and may have a HD (n-hexadecane) contact angle of 100° or less, 90° or less, or 75° or less. A HD contact angle of the liquid repellent compound of the lower limit or more can impart good liquid-repellency (in particular oil-repellency) to a substrate. The HD contact angle is a static contact angle of the liquid repellent compound to a spin-coated film, which is obtained by dropping 2 µL of HD on a spin-coated film and measuring the contact angle one second after the droplet reaches the film.

[0068] The liquid repellent compound may have a water contact angle of 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more, and 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less or 90° or less. A water contact angle of the liquid repellent compound of the lower limit or more can impart good liquid-repellency (in particular water-repellency) to a substrate. The water contact angle is a static contact angle of a liquid repellent compound to a spin-coated film, which is obtained by dropping 2 µL of water on a spin-coated film and measuring the contact angle one second after the droplet reaches the film.

[0069] The liquid repellent compound is preferably a biobased compound with carbon of biobased origin. A biobased content is measured in accordance with ASTM D6866. The biobased content may be 20% or more, preferably 30% or more, more preferably 50% or more, even more preferably 60% or more, still more preferably 70% or more, and most preferably 80% or more or 90% or more, and for example, 100%. A high biobased content means that the amount of use of fossil resource materials, which are typically petroleum, is small, and a higher biobased content of the liquid repellent compound is preferred from that point of view.

[0070] The liquid repellent compound has a biodegradation as of the 180^th day of preferably 5% or more. A higher biodegradation is preferred because of small environmental load. The liquid repellent compound may have a biodegradation as of the 180^th day of, for example, 10% or more, 20% or more, 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, and preferably 30% or more, more preferably 50% or more, further preferably 70% or more, and most preferably 80% or more. The liquid repellent compound has a biodegradation as of the 60^th day of preferably 5% or more. A higher biodegradation is preferred because of small environmental load. The liquid repellent compound may have a biodegradation as of the 60^th day of, for example, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, or 45% or more, and preferably 10% or more, and more preferably 30% or more. This biodegradation refers to the biodegradation specified in JIS K 6953-1 and ASTM D6400.

[0071] The liquid repellent compound may have a melting point of 30°C or more, 40°C or more, 60°C or more, 80°C or more, 100°C or more, or 120°C or more, and is preferably 40°C or more, and may have a melting point of 250°C or less, 225°C or less, 200°C or less, 150°C or less, 130°C or less, 120°C or less, 110°C or less, 100°C or less, 80°C or less, or 50°C or less.

[Structure]

[0072] The liquid repellent compound in the present disclosure may not have any one selected from the group consisting of a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group, a fluoroalkyl group, and a fluorine atom. The liquid repellent compound can impart liquid-repellency without including these fluorine-containing groups to a substrate.

[0073]  The liquid repellent compound may be a compound having a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent. The liquid repellent compound may have a hydrocarbon group having 6 or more and 40 or less carbon atoms (e.g., an aliphatic hydrocarbon group) from the viewpoint of liquid repellency.

(Monovalent hydrocarbon group optionally having a substituent)

[0074] The liquid repellent compound may have a monovalent hydrocarbon group optionally having a substituent.

[0075] The hydrocarbon group may be a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is particularly preferably an aliphatic hydrocarbon group. The hydrocarbon group may be branched, cyclic or linear, and preferably linear.

[0076] The hydrocarbon group may have 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, 18 or more, 20 or more, or 22 or more, preferably 6 or more, 10 or more, 12 or more, or 16 or more carbon atoms, and 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, 25 or less, or 20 or less carbon atoms.

[0077] The hydrocarbon group may have a substituent, but is preferably non-substituted. Examples of substituents include -OR', -N(R')₂, -COOR', and a halogen atom (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon group having a substituent, the amount of carbon atom relative to the carbon atom and the heteroatom may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less. The hydrocarbon group may have 1 to 3 (for example, 1) -OR' (in particular, - OH) as a substituent (for example at a site other than the end).

[0078] It is preferable that the liquid-repellent compound in the present disclosure is not a fatty acid ester having a glycoside bond. The fatty acid ester having a glycoside bond is typically a compound obtained by adding fatty acid to the hydroxy group of a compound with a structure having a glycoside bond (typically sugar (monosaccharide or polysaccharide)) via an ester bond. Use of such fatty acid ester is not preferred because liquid-repellency may be reduced.

[Examples of liquid repellent compound]

[0079] Examples of liquid repellent compounds include a compound having a hydrocarbon group having 6 or more and 40 or less carbon atoms. Examples of hydrocarbon groups and preferred ranges are as described above.

[0080] The liquid-repellent compound may be a compound having at least one group selected from the group consisting of

        -OC(=O)R, -COOR, -NHCOR and -CONHR

[wherein R is each independently a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent].

[0081] The liquid repellent compound may include an ester group, an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfone amide group, a sulfone urea group, a sulfone urethane group or a sulfone imide group (e.g., an ester group, an amide group, a urethane group, a urea group, an imide group). For example, the liquid repellent compound may include - C(=O)-O-, -O-C(=O)-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO₂NR'- wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms. The liquid repellent compound may be a compound in which a raw material compound and a modifying group (in particular the above monovalent hydrocarbon group optionally having a substituent) are bonded through at least one of the above groups. The liquid repellent compound may include an amide structure. Inclusion of at least the amide structure in the liquid repellent compound may improve liquid repellency. Herein the amide structure may be an amide structure in the broad sense, and may be selected from the amide structure in an amide (acid amide) group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfone amide group, a sulfone urethane group, a sulfone urea group and a sulfone imide group. The amide structure may be selected from the group consisting of -(C=O)N(-)₂, -(C=S)N(-)₂ and - S(=O)₂N(-)₂ (each group may be left-right inverted). In this regard, of the bonds possessed by N in the amide structure, at least one may be bonded to a hydrogen atom. The amide structure is preferably -(C=O)N(-)₂, and may be an amide structure in a group selected from the group consisting of an amide group, a urethane group, a urea group and an imide group.

[0082] More specific examples of the liquid-repellent compound include a compound formed by modifying amine, polyol or polycarboxylic acid with a hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent. In the present description, the respective compounds are also called a modified body of amine, a modified body of polyol and a modified body of polycarboxylic acid, which will be detailed separately.

[Amount of liquid-repellent compound]

[0083] The amount of the liquid-repellent compound may be 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, and 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight or less in the repellent. The liquid repellent compound alone may be used as a repellent.

{Modified body of amine}

[0084] The modified body of amine will be described as an example of the liquid repellent compound. A modified body of amine is a compound prepared by chemically modifying an amine compound so that the amine compound exhibits liquid repellency.

[0085] The modified body of amine according to the present disclosure is highly dispersible in liquid medium due to its structure, and thus the repellent of the present disclosure can have stable properties. Repellents using a polymer compound as an active ingredient tend to have a wide molecular weight distribution and contain relatively large amounts of impurity components. On the other hand, the molecular weight of the modified body of amine can be reduced and the molecular weight distribution of the modified body of amine can be narrowed (monodisperse), and this can lead to better performance.

[Structure]

[0086] The modified body of amine has a molecular weight of 200 or more, 300 or more, 350 or more, 400 or more, 500 or more, 550 or more, or 750 or more, and 3,000 or less, 2,500 or less, 2,000 or less, 1,500 or less, 1,000 or less, 900 or less, 800 or less, 750 or less, or 500 or less.

[0087] In some embodiments, the modified body of amine according to the present disclosure does not have an active hydrogen-containing group. Examples of active hydrogen-containing groups include an amino group (an amino group not adjacent to a carbonyl group, e.g., a primary or secondary amino group), a hydroxy group and a carboxyl group. In some embodiments, the modified body of amine according to the present disclosure does not have a primary or secondary amino group which is not adjacent to a carbonyl group.

[0088] The modified body of amine according to the present disclosure may be polyamide having a plurality of amide structures, and for example, may be a polyamide in which amine (a raw material amine compound, for example, polyamine) is modified with a plurality of modifying group (e.g., Z^N described below) through an amide structure. Here, amide may have an amide structure included in a urethane group, a urea group, imide and the like.

[0089] The modified body of amine may be a compound in which amine (a raw material amine compound) is modified with a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.

[0090] In the modified body of amine, one or more of amino groups in amine are replaced with a modifying group. The modifying group is preferably a monovalent hydrocarbon group optionally having a substituent. The modified body of amine may have a structure in which amine is modified by an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms from the viewpoint of the improvement in liquid-repellency.

[0091] Details of the monovalent hydrocarbon group optionally having a substituent are as described in the above (Monovalent hydrocarbon group optionally having a substituent).

(Amine backbone)

[0092] The modified body of amine according to the present disclosure has an amine backbone. The amine backbone has one or more amino groups which have a predetermined number of bonds (valence), obtained by removing a predetermined number of atoms or atomic groups (e.g., hydrogen) from an amine compound. The amino group in the amine backbone refers to a group selected from the group consisting of -NH₂, -NH- and -N(-)₂, and also includes an amino group adjacent to a carbonyl group, which is included in an amide group, a urethane group, a urea group, imide and the like. The amine backbone may be an aliphatic group or an aromatic group having one or more amino groups, and this does not exclude the presence of a heteroatom other than nitrogen.

[0093] The amine backbone may have a molecular weight of 30 or more, 50 or more, 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more, and 2,800 or less, 2,500 or less, 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, 600 or less, 450 or less, 300 or less, or 250 or less.

[0094] The amine backbone may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more and 100 or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less, and preferably 50 or less, and particularly preferably 30 or less carbon atoms.

[0095] The amine backbone has one or more amino groups. The amino group is a mono to trivalent amino group and is one or more groups selected from the group consisting of -NH₂, -NH- and -N(-)₂. The amine backbone may have 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and preferably 2 or more, and 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1 amino group.

[0096] The amine backbone has a hydrocarbon group (an aliphatic hydrocarbon group or an aromatic hydrocarbon group). The hydrocarbon group may be cyclic, branched or linear. The hydrocarbon group may be saturated or unsaturated (for example, saturated). In this case, the hydrocarbon group may be interrupted by an oxygen atom and/or sulfur atom, and may be composed of only a carbon atom, a nitrogen atom and a hydrogen atom. The hydrocarbon group may be a hydrocarbon group optionally interrupted by an oxygen atom and/or a sulfur atom (e.g., a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 or 2 hydrocarbon aromatic rings), a usual hydrocarbon group (e.g., a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 or 2 hydrocarbon aromatic rings). When the hydrocarbon group is interrupted by an oxygen atom and/or a sulfur atom, the amine backbone has an ether, thioether, polyether or polythioether structure. The amine backbone may have 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1 hydrocarbon group.

[0097] The amine backbone may be composed of mono to trivalent amino group and a chain saturated aliphatic hydrocarbon group or aromatic hydrocarbon group optionally interrupted by an oxygen atom and/or a sulfur atom.

[0098] The molar ratio between the carbon atom and the nitrogen atom (C/N ratio) in the amine backbone may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more, and may be 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 or less, and preferably 6 or less or 4 or less.

( -Y^N-Z^N_n)

[0099] The modified body of amine according to the present disclosure has one or more groups represented by the following formula:

        -Y^N-Z^N_n

[wherein Y^N is a direct bond or a 1+n valent group,

Z^N is a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and

n is an integer of 1 or more and 3 or less], and

at least one -Y^N-Z^N_n is optionally bonded to the nitrogen atom of the amine backbone.

[0100] The modified body of amine may have 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and is preferably 2 or more, and may have 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1 -Y^N-Z^N_n.

[0101] At least one -Y^N-Z^N_n in the modified body of amine is bonded to the nitrogen atom of the amine backbone. The proportion of the number of -Y^N-Z^N_n bonded to the nitrogen atom of the amine backbone to the total number of -Y^N-Z^N_n in the modified body of amine may be 10% or more, 30% or more, 60% or more, 80% or more, or 100%, and may be 100% or less, 95% or less, 75% or less, 50% or less, or 25% or less. -Y^N-Z^N_n not bonded to the nitrogen atom of the amine backbone is optionally bonded to another group (e.g., a hydrocarbon group) of the amine backbone.

(Y^N)

[0102] Y^N is a direct bond or a 1+n valent group, and preferably a 1+n valent group. Y^N functions as a linker connecting the amine backbone and n Z^N groups.

[0103] n is the number of Z^N bonded to Y^N, and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, and may be 3 or less, 2 or less, or 1 or less, and for example, 2 or less.

[0104] Y^N may be an aliphatic group (unsaturated aliphatic group or saturated aliphatic group) or an aromatic group.

[0105] Y^N may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, 500 or less, or 300 or less.

[0106]  Y^N may have a carbonyl group. Y^N may have one or more selected from the group consisting of an amide group, a urea group, a urethane group and an imide group. Alternatively, Y^N may form one or more selected from the group consisting of an amide group, a urea group, a urethane group and imide with the amino group in the amine backbone. Examples of the amide group, urea group, urethane group and imide group include: -O-C(=O)-NR'-,

        -NR'-C(=O)-,

        -NR'-C(=O)-O-,

        -NR'-C(=O)-NR'-

        -C(=O)-NR'-

        -C(=O)-NR'-C(=O)-

[wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 30 (e.g., 1 to 20, 1 to 10, or 1 to 4) carbon atoms]. Y^N is preferably bonded to a nitrogen atom in the amine backbone through a -(C=O)- group.

[0107] Y^N may be a 1+n valent group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)₂-, -NR'-, -C(OR')R'-, - C(OR') (-)₂, -N(-)₂, a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent to tetravalent hydrocarbon aromatic ring and a divalent to tetravalent heterocyclic ring wherein R' is a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms.

[0108] Y^N may be a 1+n valent group composed of one or more selected from the group consisting of Y^N1 and Y^N2,

Y^N1 may be a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, -C(=NR')-, -S-, -S(=O)₂-, -C(=S)-, -NR'-, -C(OR')R'-, - C(OR') (-)₂ and -N(-)₂ (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms),

Y^N2 may be a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent to tetravalent hydrocarbon aromatic ring, and a divalent to tetravalent heterocyclic ring. In the present description, the left side of the group represented by Y^N is bonded to the amine backbone and the right side thereof is bonded to Z^N.

o Y^N1

[0109] Y^N1 is a non-hydrocarbon linker

[0110] Y^N1 is a direct bond or a divalent or higher valent group. Y^N1 may have a valence of 2 to 4, 2 or 3, or 2. It is preferable that Y^N1 is not limited to direct bond.

[0111]  Y^N1 may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, or 500 or less.

[0112] Y^N1 may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, - C(=NR')-, -S-, -S(=O)₂-, -C(=S)-, -NR'-, -C(OR')R'-, - C(OR') (-)₂, -N(-)₂ (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms). Examples of Y^N1 include:

a direct bond,

        -O-,

        -O-C(=O)-,

        -O-C(=O)-O-,

        -O-C(=O)-NR'-,

        -NR'-,

        -NR'-C(=O)-,

        -NR'-C(=O)-O-,

        -NR'-C(=O)-NR'-,

        -C(=O)-,

        -C(=O)-O-,

        -C(=O)-NR'-,

        -C(=O)-NR'-C(=O)-,

        -C(=NR')-,

        -S-,

        -SO₂-,

        -SO₂NR'-,

        -C(OR')R'-,

        -C(OR')(-)₂,

        -N(-)₂

[wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms]. When Y^N1 is bonded to the nitrogen atom of the amine backbone, the nitrogen atom is regarded as a part of the amine backbone (an amino group).

∘ Y^N2

[0113] Y^N2 is a hydrocarbon optionally having a substituent, a hydrocarbon aromatic ring optionally having a substituent or a heterocyclic linker optionally having a substituent.

[0114] Y^N2 may be a hydrocarbon group or a non-hydrocarbon group (including a heteroatom). Y^N2 may be aliphatic or aromatic. Y^N2 may be linear, branched or cyclic.

[0115] Y^N2 is a divalent or higher valent group. Y^N2 may have a valence of, for example, 2 to 4, 2 or 3, or 2.

[0116] Y^N2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, and 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less carbon atoms.

[0117] Y^N2 is composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent.

[0118] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched or linear hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The aliphatic hydrocarbon group having 1 to 40 carbon atoms may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more carbon atoms, and 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less carbon atoms. The aliphatic hydrocarbon group may have a valence of 2 or more, 3 or more, or 4, and 4 or less, 3 or less, or 2.

[0119] The aliphatic hydrocarbon group may have a substituent. Examples of substituents include -OR', - N(R')₂, -COOR', and a halogen atom (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may have or be free of active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atom relative to the amount of carbon atom and heteroatom may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and is preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0120] Examples of the divalent to tetravalent hydrocarbon aromatic ring include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12 and preferably 5 to 12. The hydrocarbon aromatic ring may have a valence of 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0121] The hydrocarbon aromatic ring may have a substituent. Examples of substituents include -R', -OR', -N(R')₂, -COOR' and a halogen atom (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may have or be free of active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic ring having a substituent, the amount of carbon atom relative to the amount of carbon atom and heteroatom may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and is preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0122] The divalent to tetravalent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocyclic rings include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, and the like. The number of ring constituting atom of the heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12 and preferably 5 to 12. A valence of the heterocyclic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0123] The heterocyclic ring may have a substituent. Examples of substituents include -R', -OR', -N(R')₂, - COOR' and a halogen atom (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocyclic ring having a substituent, the amount of carbon atom relative to the carbon atom and the heteroatom may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and for example 65 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0124] Examples of Y^N2 include

        -Ali-

        -Cy-

        -Ali(-)₂

        -Cy(-)₂

        (-)₂Ali-

        (-)₂Cy-

        (-)₂Ali(-)₂

        (-)₂Cy(-)₂

        -Ali-Cy-

        -Cy-Ali-

        -Cy-Ali-Cy-

        -Ali-Cy-Ali-

[wherein Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and Cy is a hydrocarbon aromatic ring or a heterocyclic ring].

[0125] Specific examples of Y^N2 include:

• (CH₂)_p- (p is 1 to 40, 1 to 20, or 1 to 10),

  a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond,

  a branched hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, and

• (CH₂)_q-Cy-(CH₂)_r- (q and r are each independently 0 to 20, for example, 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring).

· Examples of Y^N

[0126] Examples of Y^N will be described. In the following, R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms.

[0127]  When Y^N is divalent, examples of Y^N include -Y^N1-, - Y^N1-Y^N2-, -Y^N1-Y^N2-Y^N1-, -Y^N1-Y^N2-Y^N1-Y^N2-, -Y^N2-, -Y^N2-Y^N1-, - Y^N2-Y^N1-Y^N2- and -Y^N2-Y^N1-Y^N2-Y^N1-.

[0128] When Y^N is trivalent, examples of Y^N include -Y^N1(-)₂, -Y^N1-Y^N2(-)₂, -Y^N1-(YN2-)₂, Y^N1-Y^N2-Y^N1(-)₂, -Y^N1-Y^N2(-Y^N1-)₂, - Y^N1-(Y^N2-Y^N1-)₂, -Y^N1-Y^N2-Y^N1-Y^N2(-)₂, -Y^N1-Y^N2-Y^N1-(Y^N2-)₂, -Y^N1-Y^N2-(Y^N1-Y^N2-)₂, -Y^N1-(Y^N2-Y^N1-Y^N2-)₂;
-Y^N2(-)₂, -Y^N2-Y^N1(-)₂, -Y^N2-(Y^N1-)₂, -Y^N2-Y^N1-Y^N2(-)₂, -Y^N2-Y^N1(-Y^N2-)₂, -Y^N2-(Y^N1-Y^N2-)₂, -Y^N2-Y^N1-Y^N2-Y^N1(-)₂, -Y^N2-Y^N1-Y^N2-(Y^N1-)₂, -Y^N2-Y^N1-(Y^N2-Y^N1-)₂, and -Y^N2-(Y^N1-Y^N2-Y^N1-)₂.

[0129] When Y^N is tetravalent, examples of Y^N include - Y^N1(-)₃, -Y^N1-Y^N2(-)₃, -Y^N1-(Y^N2-)₃, -Y^N1-Y^N2-Y^N1(-)₃, -Y^N1-Y^N2(-Y^N1-)₃, -Y^N1-(Y^N2-Y^N1-)₃, -Y^N1-Y^N2-Y^N1-Y^N2(-)₃, -Y^N1-Y^N2-Y^N1-(Y^N2-)₃, -Y^N1-Y^N2- (y^N1-y^N2-)₃, -Y^N1-(Y^N2-Y^N1-Y^N2-)₃;
-Y^N2(-) ₃, -Y^N2-Y^N1(-)₃, -Y^N2-(Y^N1-)₃, -Y^N2-Y^N1-Y^N2(-)₃, -Y^N2-Y^N1(-Y^N2-)₃, -Y^N2-(Y^N1-Y^N2-)₃, -Y^N2-Y^N1-Y^N2-Y^N1(-)₃, -Y^N2-Y^N1-Y^N2-(Y^N1-)₃, -Y^N2-Y^N1-(Y^N2-Y^N1-)₃, and -Y^N2-(Y^N1-Y^N2-Y^N1-)₃.

[0130] Preferred examples of Y^N include -Y^N1-, -Y^N1-Y^N2-, - Y^N1-Y^N2-Y^N1-, -Y^N1-Y^N2(-)₂,
-Y^N2-, -Y^N2-Y^N1-, -Y^N2-YN1-Y^N2-, -Y^N2-Y^N1(-)₂. It is preferable that in the modified body of amine, there is - (C=O)- at the end of the amine backbone in one or more Y^N, and one or more Y^N is bonded to the nitrogen atom in the amine backbone.

[0131] Y^N is preferably -Y^N1-, -Y^N1-Y^N2-, -Y^N1-Y^N2-Y^N1-, -Y^N1-Y^N2(-)₂,

        -Y^N2-, -Y^N2-Y^N1-, -Y^N2-Y^N2-, -Y^N2-Y^N1(-)₂,

[wherein Y^N1 is independently at each occurrence a direct bond,

        -O-,

        -O-C(=O)-,

        -O-C(=O)-O-,

        -O-C(=O)-NR'-,

        -NR'-,

        -NR'-C(=O)-,

        -NR'-C (=O) -O-,

        -NR'-C(=O)-NR'-,

        -C(=O)-,

        -C(=O)-O-,

or

        -C(=O)-NR'-

        -C(=O)-NR'-C(=O)-

(wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms), and

Y^N2 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a divalent aromatic group (for example, a divalent phenyl group or a divalent triazole group)]. By this, excellent liquid-repellency is imparted to substrates.

[0132]  Specific examples of Y^N also include:

        *-(C=O)-

        -O-(C=O)-NR'-

[wherein * means a bond to a nitrogen atom in the amine backbone,
R' is a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms.]

(Z^N)

[0133] Z^N is a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent. The same explanation in the above (Monovalent hydrocarbon group optionally having a substituent) applies.

[Examples of modified body of amine]

(Example 1 of modified body of amine)

[0134] An example of the modified body of amine is (Example 1 of modified body of amine), which is a compound represented by the following formula:

        N(-Y^N-Z^N_n)_p(-H)q-L¹-[N(-Y^N-Z^N_n)_r(-H)_s-L¹-]_t-N(-Y^N-Z^N_n)_p(^-H)_q

[wherein Y^N is independently at each occurrence a direct bond or a 1+n valent group,

Z^N is independently at each occurrence a linear or branched monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent,

L¹ is independently at each occurrence a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms or an aromatic hydrocarbon group which are optionally interrupted by an oxygen atom and/or a sulfur atom,

n is independently at each occurrence an integer of 1 or more and 3 or less,

p is independently at each occurrence an integer of 0 or more and 2 or less,

q is independently at each occurrence an integer of 0 or more and 2 or less,

p + q is 2 in each N(-Y^N-Z^N_n)_p(-H)_q,

r is independently at each occurrence 0 or 1,

s is independently at each occurrence 0 or 1,

r + s is 1 in each N(-Y^N-Z^N_n)_p(-H)_q,

the sum of all p and all r is 1 or more and

t is an integer of 0 or more and 10 or less].

[0135] In Example 1 of the modified body of amine, the details of Y^N, Z^N and n are as described above.

[0136] In Example 1 of the modified body of amine, L¹ is a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms or an aromatic hydrocarbon group which are optionally interrupted by an oxygen atom and/or a sulfur atom, and may be a cyclic, branched or linear hydrocarbon group, and is preferably a chain hydrocarbon group or an aromatic hydrocarbon. L¹ may be the hydrocarbon group described in the above [Amine backbone]. The hydrocarbon group may be interrupted by an oxygen atom and/or sulfur atom, may be composed of only a carbon atom, a nitrogen atom and hydrogen atom. L¹ may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group with 1 or 2 hydrocarbon aromatic rings. L¹ is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, or thioether sulfur). Specific examples thereof include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyl ether diyl group, diphenyl thioether diyl group. L¹ has 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less carbon atoms.

[0137] In Example 1 of the modified body of amine, p is independently at each occurrence an integer of 0 or more and 2 or less, q is independently at each occurrence an integer of 0 or more and 2 or less, and p + q is 2 in each N(-Y^N-Z^N_n)_p(-H)_q. Preferably p is independently at each occurrence an integer of 1 or more and for example, 2.

[0138] In Example 1 of the modified body of amine, r is independently at each occurrence 0 or 1, s is independently at each occurrence 0 or 1, and r + s is 1 in each N(-Y^N-Z^N_n)_r(-H)_s. Preferably p is independently at each occurrence an integer of 1 or more and for example, 2.

[0139] The sum of all p and all r is 1 or more, which means that Example 1 of the modified body of amine has one or more -Y^N-Z^N_n. The sum of all p and all r may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, 12 or more (the sum of all q and s may be 0), and may be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.

[0140] In Example 1 of the modified body of amine, t is an integer of 0 or more and 10 or less. t may be 0 or more, 1 or more, 2 or more, 4 or more, or 6 or more, and is preferably 0 or more or 2 or more and t may be 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1 or less, and for example 0 or 1.

(Example 2 of modified body of amine)

[0141] Another example of the modified body of amine is (Example 2 of modified body of amine), which is a compound represented by the formula:

        N(-Y^N-Z^N_n)_p(-H)_q-L²(-Y^N-Z^N_n)_u

[wherein Y^N is independently at each occurrence a direct bond or a 1+n valent group,

Z^N is independently at each occurrence a linear or branched monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent,

L² is a 1 + u valent aliphatic hydrocarbon group having 2 to 20 carbon atoms or an aromatic hydrocarbon group which are optionally interrupted by an oxygen atom and/or a sulfur atom,

n is independently at each occurrence an integer of 1 or more and 3 or less,

p is an integer of 0 or more and 2 or less,

q is an integer of 0 or more and 2 or less,

p + q is 2,

u is an integer of 1 or more and 3 or less, and

the sum of p and u is 1 or more].

[0142] In Example 2 of the modified body of amine, the details of Y^N, Z^N_n and n are as described above.

[0143] In Example 2 of the modified body of amine, L² is a 1+u valent aliphatic hydrocarbon group having 2 to 20 carbon atoms or an aromatic hydrocarbon group which are optionally interrupted by an oxygen atom and/or a sulfur atom, and may be a cyclic, branched or linear hydrocarbon group, and is preferably a chain hydrocarbon group or an aromatic hydrocarbon. L² may be the hydrocarbon group described in the above [Amine backbone]. The hydrocarbon group may be interrupted by an oxygen atom and/or sulfur atom, may be composed of only a carbon atom, a nitrogen atom and hydrogen atom. L² may be, for example, a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group with 1 or 2 hydrocarbon aromatic rings. L² is preferably a cyclic group having both a ring (e.g., an aromatic ring) and a chain structure (e.g., a linear structure, ether oxygen, or thioether sulfur). Specific examples thereof include 1,3-phenylenebisalkylene group, 1,4-phenylenebisalkylene group, diphenyl ether diyl group, diphenyl thioether diyl group. L² has 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more, and 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less carbon atoms.

[0144] In Example 2 of the modified body of amine, p is an integer of 0 or more and 2 or less, q is an integer of 0 or more and 2 or less, and p + q is 2. p may be preferably 1 or more and for example, 2.

[0145] In Example 2 of the modified body of amine, u is an integer of 1 or more and 3 or less. u is 1, 2 or 3, and for example 2 or 3.

[0146] In Example 2 of the modified body of amine, the sum of p and u is 1 or more, which means that Example 2 of the modified body of amine has one or more -Y^N-Z^N_n. The sum of all p and all u may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the sum of all q may be 0), and the sum of p and u may be 5 or less, 4 or less, 3 or less, or 2 or less.

(Specific Examples)

[0147] Specific examples of modified bodies of amine include the compounds represented by the following formula. In the following formula, the details of Z are as described above for Z^N.

[0148] The modified body of amine may be a synthesized wax derived from animal or vegetable oil and fat. The synthesized wax may also be prepared by condensing fatty acid derived from animal or vegetable oil and fat and aliphatic amine or amine containing aromatic. Examples of synthetic wax include a fatty acid amide compound such as a hydroxy fatty acid amide compound, a palmitamide compound, an octadecanoic acid amide compound, a stearic acid amide compound, an arachidic acid amide compound, a behenic acid amide compound, a lignoceric acid amide compound, an oleic acid amide compound, a linoleic acid amide compound, an α-linolenic acid amide compound, γ-linolenic acid amide compound, an arachidonic acid amide compound, an icosapentaenoic acid amide compound and a docosahexaenoic acid amide compound.

[Production Method]

[0149] The method for producing the modified body of amine is not limited, and examples thereof include a method in which a modified body of amine is synthesized by allowing various types of amines (raw material amines) to react with a Z^N group-containing carboxylic acid in the presence of a condensing agent, if necessary, and a method in which a modified body of amine is synthesized by allowing amines to react with Z^N group-containing carboxylic acid chloride, acid anhydride, isocyanate or the like. A known condensing agent may be used, and examples thereof include DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA and Py-Bop.

(Amine (raw material amine))

[0150] Examples of amine (raw material amine), which is a precursor of amine backbone, include those capable of forming amine backbone, such as alkylamine such as methylamine, ethylamine, propylamine, butylamine and dibutylamine; alkylenediamine such as ethylenediamine, propylenediamine, butylenediamine, pentanediamine, hexamethylenediamine, cyclohexanediamine and methylenebiscyclohexylamine; polyalkylenepolyamine such as diethylenetriamine, triethylenetetramine, tris (2-aminoethyl) amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris (2-aminopropyl) amine, tetrapropylenepentamine, pentapropylenehexamine, iminobispropylamine, dibutylenetriamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl) ether, bis [2-(2-aminoethoxy)ethyl] ether, bis[2-(3-aminoprotoxy)ethyl] ether, spermine and spermidine; oxygen or sulfur-containing aliphatic amine such as 1-aminopropanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, polyoxypropylenediamine and polyoxyethylenediamine; aromatic monoamine such as aniline, 1- or 2-naphthylamine, 1-, 2-, or 9-aminoanthracene, 9-aminophenanthracene and 2-, 3- or 4-aminobiphenyl; monocyclic aromatic polyamine such as o-, m- or p-phenylene diamine, o-, m- or p-xylylenediamine, diaminotoluene and 2,3-, 2,4- or 2,5-tolylenediamine; polycyclic aromatic polyamine such as diaminobiphenyl, bisaminophenoxyphenylpropane, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenylsulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenyl hexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoyl benzene, bisaminodimethylbenzyl benzene, aminophenoxybiphenyl, aminophenoxyphenyl ketone, bisaminoditrifluoromethylbenzyl benzene, aminophenoxyphenyl sulfone, aminophenoxyphenyl ether, aminophenoxyphenyl propane, bis(aminophenoxybenzoyl) benzene, bis(aminophenoxy-α,α-dimethylbenzyl) benzene, bis[(aminoaryloxy)benzoyl] diphenylether, bis (amino-α,α-dimethylbenzylphenoxy) benzophenone, aminophenoxyphenyl sulfide, bis [amino-α,α-dimethylbenzylphenoxy]diphenyl sulfone, 4,4'-bis[aminophenoxyphenoxy]diphenyl sulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminotriphenyl methane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-methylenebisaniline, 4,4'-oxydianiline, 1,3-bis(4-aminophenoxy)benzene, 4,4'-diaminodiphenylether and 4,4'-bis(aminophenyl)amine; oxygen or sulfur-containing polycyclic aromatic polyamine such as 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenylsulfide; and hydroxyl group-containing polyamine such as 2-hydroxyethylethylenediamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine and di-2-hydroxypropylethylenediamine. Polyamine may also be a polymer of a polymerizable compound such as allylamine.

{Modified body of polyol}

[0151] The modified body of polyol will be described as an example of the liquid repellent compound. A modified body of polyol is a compound prepared by chemically modifying polyol so that the polyol exhibits liquid repellency.

[Structure]

[0152] The modified body of polyol may be a polymer having a degree of polymerization of 1 or more. The modified body of polyol may have a degree of polymerization of 2 or more, 3 or more, 5 or more, 6 or more, preferably 7 or more, more preferably 8 or more, and further preferably 9 or more from the viewpoint of the improvement in the liquid-repellency. The modified body of polyol may have a degree of polymerization of 100 or less, preferably 50 or less, more preferably 30 or less, further preferably 15 or less from the viewpoint of the improvement in handling properties of the repellent. The degree of polymerization means the repeating number of monomer units constituting the polymer.

[0153] The degree of polymerization in the present disclosure means an average degree of polymerization. The average degree of polymerization in the present disclosure is measured under the following conditions.

[0154] When the modified body of polyol in the present disclosure is a modified body of polyglycerol obtained by modifying polyglycerol, the degree of polymerization of the modified body of polyol means the average degree of polymerization of the polyglycerol. The average degree of polymerization of polyglycerol refers to an average degree of polymerization (n) calculated from the hydroxyl number determined by the end group analysis. More specifically, the average degree of polymerization and the average molecular weight are calculated from the following (Formula 1) and (Formula 2).

Hydroxyl number = 56110 (n+2) / average molecular weight

[0155] The hydroxyl number in the above (Formula 2) indicates the number of hydroxyl groups in polyglycerol. The hydroxyl number is calculated from the amount of potassium hydroxide necessary for neutralizing acetic acid used for acetylation of free hydroxyl groups contained in 1 g of polyglycerol, which is determined according to The JOCS Standard Methods for the Analysis of Fats, Oils and Related Materials (I), 2003, edited by Japan Oil Chemists' Society. The hydroxyl number of polyglycerol, which is the raw material, is actually measured by the above Standard Methods for the Analysis of Fats, Oils and Related Materials, and the average degree of polymerization and the average molecular weight of polyglycerol may be calculated by the above relational expression.

[0156] When the modified body of polyol in the present disclosure is a modified body of polyvinyl alcohol obtained by modifying polyvinyl alcohol, the degree of polymerization of the modified body of polyol means the average degree of polymerization of the polyvinyl alcohol. The average degree of polymerization of polyvinyl alcohol may be measured according to JIS K 6726, Testing Methods for Polyvinyl Alcohol.

[0157] When the modified body of polyol in the present disclosure is a modified body of polysaccharide obtained by modifying polysaccharide, the degree of polymerization of the modified body of polyol means the average degree of polymerization of the polysaccharide. The average degree of polymerization of polysaccharide may be analyzed as follows. The degree of polymerization refers to the number of monosaccharide units in polysaccharide (fructose and glucose units), and the average degree of polymerization means the maximum of the peaks in the results of analysis obtained by a common analytical method such as HPLC, GC or HPAEC as described below. The average degree of polymerization may be measured by using ULTRON PS-80N made by Shinwa Chemical Industries Ltd. (8 × 300 mm) (solvent: water, flow rate: 0.5 ml/ minute, temperature: 50°C) or TSK-GEL G30000 PWXL made by Tosoh Corporation (7.8 × 300 mm) (solvent: water, flow rate: 0.5 ml/ minute, temperature: 50°C) as the column, and a differential refractometer as the detector.

[0158] The modified body of polyol may be a low molecular weight compound (having a weight average molecular weight of less than 1,500, less than 1,000 or 500 or less) and/or a high molecular weight compound. The modified body of polyol may have a weight average molecular weight of 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may have a weight average molecular weight of 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0159] The hydroxy group substitution ratio of the modified body of polyol may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, preferably 10% or more, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, and for example, 95% or less. The "substitution ratio" means the proportion (mol%) of modified hydroxy groups out of the hydroxy groups derived from polyol, and may mean the proportion (mol%) of hydroxy groups modified by a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.

[0160] The residual ratio of hydroxyl groups in the modified body of polyol may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, and for example, is 5% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, and for example, 50% or less, 30% or less, or 10% or less. In this regard, the "residual ratio" means the proportion (mol%) of hydroxyl groups without modification, out of the hydroxy groups derived from the polyol.

[0161] The number of modifying groups that the modified body of polyol has may be 2 or more, 5 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 15 or more, 30 or more, or 50 or more, and may be 1,000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. In this regard, the modifying group is preferably a monovalent hydrocarbon group optionally having a substituent.

[0162] The modifying group equivalent of the modified body of polyol may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1,000 or more, and may be 2,500 or less, 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, 500 or less, or 400 or less. The modifying group equivalent is obtained by dividing the weight average molecular weight of modified body of polyol by the number of modifying groups. In this regard, the modifying group is preferably a monovalent hydrocarbon group optionally having a substituent.

[0163] In the modified body of polyol, one or more of hydroxy groups in polyol are substituted by a modifying group. The modifying group is preferably a monovalent hydrocarbon group optionally having a substituent. The modified body of polyol may have a structure in which polyol is modified by an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms from the viewpoint of the improvement in liquid-repellency.

[0164] Details of the monovalent hydrocarbon group optionally having a substituent are as described in the above (Monovalent hydrocarbon group optionally having a substituent).

(-Y^O-Z^O_n)

[0165] In the modified body of polyol in the present disclosure, one or more hydroxy groups in polyol are optionally substituted by a group represented by the following formula:

        -Y^O-Z^O_n

[wherein Y^O is a 1+n valent group composed of one or more selected from the group consisting of Y^O1 and Y^O2,

Y^O1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, - C(=NR')-, -S-, -S(=O)₂-, -C(=S)-, -NR'-, -C(OR')R'-, - C(OR') (-)₂ and -N(-)₂ (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms),

Y^O2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent,

Z^O is a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and

n is an integer of 1 or more and 3 or less].

(Y^O)

[0166] 

Y^O is a 1+n valent group composed of one or more selected from the group consisting of Y^O1 and Y^O2,

Y^O1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, - C(=NR')-, -S-, -S(=O)₂-, -C(=S)-, -NR'-, -C(OR')R'-, - C(OR')(-)₂ and -N(-)₂ (wherein R' is independently at each occurrence a hydrogen atom or hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms),

Y^O2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent.

[0167]  n is the number of Z^O bonded to Y^O, and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more, and 3 or less, 2 or less, or 1 or less, and for example, 2 or less.

[0168] Y^O may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and 3,000 or less, 2,500 or less, 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0169] Y^O may include at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfone amide group, a sulfone urea group, a sulfone urethane group, or a sulfone imide group. For example, Y^O may include -C(=O)-NR'-, -C(=S)-NR'-, -O-C(=O)-NR'-, - NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO₂NR'-. Inclusion of these groups in Y^O may improve liquid repellency.

o Y^O1

[0170] Y^O1 is a non-hydrocarbon linker.

[0171] Y^O1 is a direct bond or a divalent or higher valent group. Y^O1 may have a valence of 2 to 4, 2 or 3, or 2. It is preferable that Y^O1 is not limited to direct bond.

[0172] Y^O1 may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, or 500 or less.

[0173] Y^O1 may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, - S(=O)₂-, -NR'-, -C(OR')R'- and -C(OR') (-)₂ (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms).

[0174] Examples of Y^O1 include:
a direct bond,

        -O-,

        -O-C(=O)-,

        -O-C(=O)-O-,

        -O-C(=O)-NR'-,

        -NR'-,

        -NR'-C(=O)-,

        -NR'-C(=O)-O-,

        -NR'-C(=O)-NR'-,

        -C(=O)-,

        -C(=O)-O-,

        -C(=O)-NR'-,

        -SO₂-,

        -SO₂NR'-,

        -C(OR')R'-,

and

        -C(OR')(-)₂

(wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms).

[0175] Y^O1 may include at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfone amide group, a sulfone urea group, a sulfone urethane group, or a sulfone imide group. For example, Y^O2 may include -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO₂NR'-. Inclusion of these groups in Y^O1 may improve liquid repellency.

o Y^O2

[0176] Y^O2 is a hydrocarbon optionally having a substituent, a hydrocarbon aromatic ring optionally having a substituent or a heterocyclic linker optionally having a substituent.

[0177] Y^O2 may be a hydrocarbon group or a non-hydrocarbon group (including a heteroatom). Y^O2 may be aliphatic or aromatic. Y^O2 may be linear, branched or cyclic.

[0178] Y^O2 is a divalent or higher valent group. Y^O2 may have a valence of, for example, 2 to 4, 2 or 3, or 2.

[0179] Y^O2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less carbon atoms.

[0180] Y^O2 is composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent.

[0181] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched or linear hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The aliphatic hydrocarbon group having 1 to 40 carbon atoms may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more carbon atoms, and 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less carbon atoms. The aliphatic hydrocarbon group may have a valence of 2 or more, 3 or more, or 4, and 4 or less, 3 or less, or 2.

[0182] The aliphatic hydrocarbon group may have a substituent. Examples of substituents include -OR', - N(R')₂, -COOR', and a halogen atom (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may have or be free of active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atom relative to the amount of carbon atom and heteroatom may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and is preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0183] Examples of the divalent to tetravalent hydrocarbon aromatic ring include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring constituting atom of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12, and preferably 5 to 12. The hydrocarbon aromatic ring may have a valence of 2 or more, 3 or more, or 4, and 4 or less, 3 or less, or 2.

[0184] The hydrocarbon aromatic ring may have a substituent. Examples of substituents include -R', -OR', -N(R')₂, -COOR' and a halogen atom (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may have or be free of active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic ring having a substituent, the amount of carbon atom relative to the carbon atom and the heteroatom may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and is preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0185] The divalent to tetravalent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocyclic rings include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, and the like. The number of ring constituting atom of the heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12 and preferably 5 to 12. A valence of the heterocyclic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0186] The heterocyclic ring may have a substituent. Examples of substituents include -R', -OR', -N(R')₂, - COOR' and a halogen atom (wherein R' is independently at each occurrence a hydrogen atom or hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocyclic ring having a substituent, the amount of carbon atom relative to the carbon atom and the heteroatom may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and for example 65 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0187] Examples of Y^O2 include

        -Ali-,

        -Cy-,

        -Ali(-)₂,

        -Cy(-)₂,

        (-)₂Ali-,

        (-)₂Cy-,

        (-)₂Ali(-)₂,

        (-)₂Cy(-)₂,

        -Ali-Cy-,

        -Cy-Ali-,

        -Cy-Ali-Cy-,

and

        -Ali-Cy-Ali-

[wherein Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and Cy is a hydrocarbon aromatic ring or a heterocyclic ring].

[0188] Specific examples of Y^O2 include:

-(CH₂)_p- (p is 1 to 40, 1 to 20, or 1 to 10),

a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond,

a branched hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, and

-(CH₂)_q-Cy-(CH₂)_r- (q and r are each independently 0 to 20, for example, 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring).

(Example of Y^O)

[0189] Examples of Y^O will be described. In the following, R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms.

[0190] When Y^O is divalent, examples of Y^O include -Y^O1-, - Y^O1-Y^O2-, Y^O1-Y^O2-Y^O1-, Y^O1-Y^O2-Y^O1-Y^O2-, -Y^O2-, -Y^O2-Y^O1-, - Y^O2-Y^O1-Y^O2- and -Y^O2-Y^O1-Y^O2-Y^O1-.

[0191] When Y^O is trivalent, examples of Y^O include -Y^O1(-)₂, Y^O1-Y^O2-(-)₂, -Y^O1-(Y^O2-)₂, -Y^O1-Y^O2-Y^O1(-)₂, -Y^O1-Y^O2(-Y^O1-)₂, - Y^O1-(Y^O2-Y^O1-)₂, -Y^O1-Y^O2-Y^O1-Y^O2(-)₂, -Y^O1-Y^O2-Y^O1-(Y^O2-)₂, -Y^O1-Y^O2-(Y^O1-Y^O2-)₂, -Y^O1-(Y^O2-Y^O1-Y^O2-)₂;
-Y^O2(-)₂, -Y^O2-Y^O1(-)₂, -Y^O2-(Y^O1-)₂, -Y^O2-Y^O1-Y^O2(-)₂, -Y^O2-Y^O1(-Y^O2-)₂, -Y^O2-(Y^O1-Y^O2-)₂, -Y^O2-Y^O1-Y^O2-Y^O1(-)₂, -Y^O2-Y^O1-Y^O2-(Y^O1-)₂, -Y^O2-Y^O1-(Y^O2-Y^O1-)₂, and -Y^O2-(Y^O1-Y^O2-Y^O1-)².

[0192] When Y^O is tetravalent, examples of Y^O include - Y^O1(-)₃, -Y^O1-Y^O2(-)₃, -Y^O1-(Y^O2-)₃, -Y^O1-Y^O2-Y^O1(-)₃, -Y^O1-Y^O2(-Y^O1-)₃, -Y^O1-(Y^O2-Y^O1-)₃, -Y^O1-Y^O2-Y^O1-Y^O2(-)₃, -Y^O1-Y^O2-Y^O1-(Y^O2-) ₃, -Y^O1-Y^O2-(Y^O1-Y^O2-)₃, -Y^O1-(Y^O2-Y^O1-Y^O2-)₃;
-Y^O2(-)₃, -Y^O2-Y^O1(-)₃, -Y^O2-(Y^O1-)₃, -Y^O2-Y^O1-Y^O2(-) ₃, -Y^O2-Y^O1(-Y^O2-)₃, -Y^O2-(Y^O1-Y^O2-)₃, -Y^O2-Y^O1-Y^O2-Y^O1(-)₃, -Y^O2-Y^O1-Y^O2-(Y^O1-)₃, -Y^O2-Y^O1-(Y^O2-Y^O1-)₃, and -Y^O2-(Y^O1-Y^O2-Y^O1-)₃.

[0193] Preferred examples of Y^O include -Y^O1-, -Y^O1-Y^O2-, - Y^O1-Y^O2-Y^O1-, -Y^O1-Y^O2(-)₂,
-Y^O2-, -Y^O2-Y^O1-, -Y^O2-Y^O1-Y^O2-, -Y^O2-Y^O1(-)₂.

(Preferred example of Y^O)

[0194] Y^O is preferably

        -O-Y^O11-

or

        -O-Y^O11-Y^O21-Y^O12-

[wherein, independently at each occurrence,

Y^O11 is a direct bond, -C(=O)-, -C(=O)-NR'- or - C(=S)-NR'-,

Y^O21 is a hydrocarbon group having 1 to 40 carbon atoms, and

Y^O12 is -O-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO₂-, - SO₂NR'-, -C(OR')R'-, or -C(OR')(-)₂].

[0195] Y^O11 is a non-hydrocarbon linker, and is a direct bond or divalent or higher valent group.

[0196] Y^O11 may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, or 500 or less.

[0197] Y^O11 is a direct bond, -C(=O)-, -C(=O)-NR'- or - C(=S)-NR'-.

[0198] Y^O21 is a divalent hydrocarbon linker, and may be a hydrocarbon group having 1 to 40 carbon atoms.

[0199] Y^O21 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less carbon atoms.

[0200] The hydrocarbon group having 1 to 40 carbon atoms may be cyclic, branched or linear, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.

[0201] Specific examples of Y^O21 include:

-(CH₂)_p- (p is 1 to 40, 1 to 20, or 1 to 10),

a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond,

a branched hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, and

-(CH₂)_q-Cy-(CH₂)_r- (q and r are each independently 0 to 20, for example, 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring).

[0202] Y^O12 may be -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO₂-, -SO₂NR'-, - C(OR')R'- or -C(OR')(-)₂.

[0203]  Y^O12 may include at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfone amide group, a sulfone urea group, a sulfone urethane group, or a sulfone imide group. For example, Y^O12 may be -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO₂NR'-. Inclusion of these groups in Y^O12 may improve liquid repellency.

(Z^O)

[0204] Z^O is a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent. The same explanation in the above (a monovalent hydrocarbon group optionally having a substituent) applies.

[Other modifying groups]

[0205] The hydroxy group of polyol may be substituted by a modifying group other than -Y^O-Z^O_n. Examples of modifying groups include an anionic group and/ or a cationic group.

[0206] Examples of anionic groups include a monomer having a carboxyl group, a sulfonic acid group or a phosphoric acid group.

[0207] Examples of salts of the anionic group include alkaline metal salt, alkaline earth metal salt, or an ammonium salt such as methyl ammonium salt, ethanol ammonium salt and triethanol ammonium salt.

[0208] Examples of cationic groups include an amino group, which is preferably a tertiary amino group and a quaternary amino group. It is preferable that in the tertiary amino group, two groups bonded to a nitrogen atom, which are the same or different, are an aliphatic group having 1 to 5 carbon atoms (in particular alkyl group), an aromatic group having 6 to 20 carbon atoms (an aryl group), or an aromatic aliphatic group having 7 to 25 carbon atoms (in particular an aralkyl group, e.g., a benzyl group (C₆H₅-CH₂-)). It is preferable that in the quaternary amino group, three groups bonded to a nitrogen atom, which are the same or different, are an aliphatic group having 1 to 5 carbon atoms (in particular alkyl group), an aromatic group having 6 to 20 carbon atoms (an aryl group), or an aromatic aliphatic group having 7 to 25 carbon atoms (in particular an aralkyl group, e.g., benzyl group (C₆H₅-CH₂-)). In the tertiary amino group and the quaternary amino group, the last group bonded to the nitrogen atom may have a carbon-carbon double bond. The cationic group may be in the form of salt.

[0209] The cationic group in the form of salt is a salt with an acid (an organic acid or an inorganic acid). An organic acid such as a carboxylic acid having 1 to 20 carbon atoms (in particular, a monocarboxylic acid such as acetic acid, propionic acid, butyric acid and stearic acid) are preferred.

[Production Method]

[0210] The modified body of polyol may be produced by reacting a modifying agent including a modifying group (or a precursor structure of the modifying group) with the hydroxy group of polyol.

(Polyol)

[0211] Polyol has two or more hydroxy groups and is a raw material of the modified body of polyol. Polyol has two or more hydroxy groups in the molecule. Polyol may be aliphatic or aromatic, and is preferably aliphatic.

[0212] Polyol may have an ether bond. Preferably polyol may have two or more ether bonds. More specifically, polyol is preferably a compound having two or more hydroxy groups and two or more ether bonds. In other words, polyol is preferably polyether having two or more hydroxy groups.

[0213] When polyol is a polymer, polyol may have a hydroxy group and an ether bond in the repeating structure of the monomer unit.

[0214]  Polyol may be a low molecular weight compound (having a weight average molecular weight of, for example, less than 1,000 or 500 or less) and/or a high molecular weight compound. Polyol has a weight average molecular weight of 50 or more, 100 or more, 300 or more, 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0215] Polyol may have 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more hydroxy groups, and 3,000 or less, 1,000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less hydroxy groups.

[0216] The hydroxy group equivalent of polyol may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, or 150 or more, and may be 1,000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. Dividing the weight average molecular weight of polyol by the number of hydroxyl groups gives the hydroxy group equivalent of polyol.

[0217]  Polyol may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The above natural product also includes a compound converted from microorganisms. Examples of polyol include a monosaccharide, an oligosaccharide, a polysaccharide, a sugar alcohol (reducing sugar), a hydroxy acid, an amino acid, vitamin, flavonol, hydroxyhydrocarbon, a polymer of a hydroxy group-containing compound, polyether polyol, polymer polyol, polyester polyol and other polyols.

[0218] Examples of monosaccharides include glucose, fructose, galactose and xylose.

[0219] Examples of oligosaccharides include sucrose, cycloamylose, cyclodextrin, maltose, trehalose, lactose and sucralose.

[0220] Examples of sugar alcohols (reducing sugar) include sorbitol, maltitol, erythritol, isomalt, lactitol, mannitol, xylitol, sorbitan and lactitol.

[0221] Examples of polysaccharides include starch, cellulose, curdlan, pullulan, alginic acid, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa-carrageenan, iota-carrageenan, isomaltodextrin, gellan gum and tamarind seed gum.

[0222] Examples of hydroxy acids include ascorbic acid, kojic acid, quinic acid, chlorogenic acid and gluconic acid.

[0223] Examples of amino acids include glucosamine.

[0224] Examples of vitamins include ascorbic acid and inositol.

[0225] Examples of flavonols include catechin, quercetin and anthocyanin.

[0226] Examples of hydroxyhydrocarbons include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, trimethylene glycol, glycerol, trimethylolpropane and trimethylolethane. The hydroxyhydrocarbon are a hydrocarbon having a hydroxy group, and may be aliphatic or aromatic, and is preferably aliphatic. The term "hydroxyhydrocarbon" may also mean a hydroxyhydrocarbon other than the compounds included in a different group, such as polysaccharide (other hydroxyhydrocarbons).

[0227] Examples of polymers of a hydroxy group-containing compound include polyglycerol, polyvinyl alcohol, hydroxyethyl (meth)acrylate polymer, hydroxypropyl (meth)acrylate polymer and hydroxybutyl (meth)acrylate polymer.

[0228] Polyether polyol may be a compound obtained by addition polymerization of alkylene oxide onto an initiator. Examples of initiators include a bifunctional or higher functional compound having a hydroxyl group. Examples of initiators include propylene glycol, polypropylene glycol, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, trimethylol propane, triethanolamine, pentaerythritol, ethylenediamine, aromatic diamine, diethylenetriamine, sorbitol and sucrose. Alkylene oxide include ethylene oxide and propylene oxide. The polyether polyol, which is obtained by addition polymerization of alkylene oxide onto the initiator, is also referred to as polyoxyalkylene polyol, or an oxyalkylene derivative of polyol. Typical examples of polyether polyol include polyoxypropylene triol obtained by addition polymerization of propylene oxide onto glycerol and polyoxypropylene polyglyceryl ether obtained by addition polymerization of propylene oxide onto polyglycerol.

[0229] An example of polymer polyol is a compound obtained by polymerizing at least a moiety of polyether polyol in the polyether polyol with an ethylenically unsaturated monomer. Examples of ethylenically unsaturated monomers include acrylonitrile and styrene.

[0230] An example of polyester polyol may be a compound obtained by dehydration condensation of a difunctional or higher functional compound having a carboxyl group and a difunctional or higher functional compound having a hydroxyl group. Examples of difunctional or higher functional compounds having a carboxyl group include terephthalic acid, isophthalic acid, phthalic acid, methylphthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid and an acid anhydride thereof. Examples of difunctional or higher functional compounds having a hydroxyl group include ethylene glycol, propylene glycol, propanediol, neopentyl glycol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol and a polymer thereof.

(Modifying agent)

[0231] The modifying agent is preferably a compound which is reactive to polyol and comprises the above monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.

[0232]  Examples of modifying agents are as follows:

Acid halide	G(O=)C-ZO
Acid anhydride	O(C(=O)-ZO)2
Carboxylic acid	HO(O=)C-ZO
Isocyanate	O=C=N-ZO
Thioisocyanate	S=C=N-ZO
Epoxy	(CH2OCH)CH2O-ZO
Halide	G-ZO
Amine	H2N-ZO
Hydroxy	HO-ZO

[In the formula, Z^O is as described above, and G is a halogen atom (e.g., F, Cl, Br or I)].

[0233] Z^O in the structure of the above modifying agent may be replaced with any group constituting the modifying group. For example, Z^O may be a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and Z^O may be -Y^O-Z^O_n.

[0234] The modified body of polyol may also be synthesized by reacting polyol and a modifying agent. For example, the modified body of polyol may be synthesized by forming an ester bond by reacting a modifying agent, which is an acid halide compound, acid anhydride or carboxylic acid, with the hydroxy group of polyol. Alternatively, the modified body of polyol may be produced by forming an ether bond by reacting a modifying agent, which is a halide compound or an epoxy compound, with the hydroxy group of polyol. Conditions of the reaction between polyol and the modifying agent may be suitably designed by a person skilled in the art, including use of a catalyst (e.g., acid catalyst and base catalyst) and use of a condensing agent depending on the intended product.

{Modified body of polycarboxylic acid}

[0235] The modified body of polycarboxylic acid will be described as an example of the liquid repellent compound. A modified body of polycarboxylic acid is a compound prepared by chemically modifying polycarboxylic acid so that polycarboxylic acid exhibits liquid repellency.

[Structure]

[0236] The modified body of polycarboxylic acid may be a low molecular weight compound (having a weight average molecular weight of, for example, less than 1,500, less than 1,000 or 500 or less) and/or a high molecular weight compound. The modified body of polycarboxylic acid may have a weight average molecular weight of 100 or more, 200 or more, 300 or more, 400 or more, 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and may have a weight average molecular weight of 1,000,000 or less, 750,000 or less, 500,000 or less, 300,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0237] The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the modified body of polycarboxylic acid may be measured by GFC using polyethylene glycol/ polyethylene oxide as a standard sample by the following apparatus under the following conditions.

Separation column: SB-806M (8 mm × 30 mm, Shodex)

Column temperature: 40°C

Solvent for mobile phase: ion-exchanged water

Flow rate of mobile phase: 1.0 mL/min

Sample concentration: 0.5 wt%

Injection amount: 50 µL

Detector: RI detector (Waters 2414 made by Waters)

[0238] The weight average molecular weight (Mw), the number average molecular weight (Mn) and polydispersity (Mw/Mn) of the modified body of polycarboxylic acid in terms polystyrene may be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent and Shodex KF400RL and KF400RH columns (polystyrene gel) made by SHOWA DENKO K.K.

[0239]  The hydroxy group substitution ratio in the carboxyl group of the modified body of polycarboxylic acid may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 90% or more, or 100%, and is preferably 10% or more, for example, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, particularly 80% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, and is for example, 95% or less. The "substitution ratio" means the proportion (mol%) of modified hydroxy groups out of the hydroxy groups in the carboxyl group derived from polycarboxylic acid, and may mean the proportion (mol%) of hydroxy groups modified by a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.

[0240] The residual ratio of hydroxyl groups in the carboxyl group in the modified body of polycarboxylic acid may be 1% or more, 3% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, and for example, is 5% or more, and may be 100% or less, 95% or less, 85% or less, 75% or less, 65% or less, 55% or less, 45% or less, 35% or less, 25% or less, 15% or less, or 5% or less, and for example, 50% or less, 30% or less, or 10% or less. In this regard, the "residual ratio" means the proportion (mol%) of hydroxyl groups without modification, out of the hydroxy groups in the carboxyl group derived from polycarboxylic acid.

[0241] The number of modifying groups that the modified body of polycarboxylic acid has may be 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, or 50 or more, and may be 1,000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less. In this regard, the modifying group is preferably a monovalent hydrocarbon group optionally having a substituent.

[0242] The modifying group equivalent of the modified body of polycarboxylic acid may be 150 or more, 250 or more, 350 or more, 450 or more, 550 or more, 650 or more, 750 or more, or 1,000 or more, and may be 2,500 or less, 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, 500 or less, or 400 or less. The modifying group equivalent is obtained by dividing the weight average molecular weight of modified body of polycarboxylic acid by the number of modifying groups. In this regard, the modifying group is preferably a monovalent hydrocarbon group optionally having a substituent.

[0243]  In the modified body of polycarboxylic acid, one or more of hydroxy groups in polycarboxylic acid are substituted by a modifying group. The modifying group is preferably a monovalent hydrocarbon group optionally having a substituent. In the modified body of polycarboxylic acid, polycarboxylic acid may have an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms from the viewpoint of the improvement in liquid repellency.

[0244] Details of the monovalent hydrocarbon group optionally having a substituent are as described in the above (Monovalent hydrocarbon group optionally having a substituent).

(-Y^C-Z^C_n)

[0245] In the modified body of polycarboxylic acid in the present disclosure, one or more hydroxyl groups in the carboxyl group in polycarboxylic acid are substituted by a group represented by the following formula: -Y^C-Z^C_n [wherein Y^C is a 1+n valent group composed of one or more selected from the group consisting of Y^C1 and Y^C2,

Y^C1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, - C(=NR')-, -S-, -S(=O)₂-, -C(=S)-, -NR'-, -C(OR')R'-, - C(OR') (-)₂ and -N(-)₂ (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms),

Y^C2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent,

Z^C is a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and

n is an integer of 1 or more and 3 or less].

(Y^C)

[0246] 

Y^C is a 1+n valent group composed of one or more selected from the group consisting of Y^C1 and Y^C2,

Y^C1 is a group composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, - C(=NR')-, -S-, -S(=O)₂-, -C(=S)-, -NR'-, -C(OR')R'-, - C(OR')(-)₂ and -N(-)₂ (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms),

Y^C2 is a group composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent,

[0247] n is the number of Z^C bonded to Y^C, and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, and for example, 2 or less.

[0248] Y^C may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more, and 3,000 or less, 2,500 or less, 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, 500 or less, 300 or less, 200 or less, 100 or less, or 50 or less.

[0249] Y^C may include at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfone amide group, a sulfone urea group, a sulfone urethane group, or a sulfone imide group. For example, Y^C may be -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO₂NR'-. Inclusion of these groups in Y^C may improve liquid repellency.

∘ Y^C1

[0250] Y^C1 is a non-hydrocarbon linker.

[0251] Y^C1 is a direct bond or a divalent or higher valent group. Y^C1 may have a valence of 2 to 4, 2 or 3, or 2. It is preferable that Y^C1 is not limited to direct bond.

[0252] Y^C1 may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, or 500 or less.

[0253] Y^C1 may be composed of one or more selected from the group consisting of a direct bond, -O-, -C(=O)-, - S(=O)₂-, -NR'-, -C(OR')R'-, and -C(OR')(-)₂, (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms). Examples of Y^C1 include: a direct bond,

        -O-,

        -O-C(=O)-,

        -O-C(=O)-O-,

        -O-C(=O)-NR'-,

        -NR'-,

        -NR'-C(=O)-,

        -NR'-C(=O)-O-,

        -NR'-C(=O)-NR'-,

        -C(=O)-,

        -C(=O)-O-,

        -C(=O)-NR'-,

        -SO₂-,

        -SO₂NR'-,

        -C(OR')R'-,

and

        -C(OR')(-)₂.

(wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms.)

[0254] Y^C1 may include at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfone amide group, a sulfone urea group, a sulfone urethane group, or a sulfone imide group. For example, Y^C2 may include -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO₂NR'-. Inclusion of these groups in Y^C1 may improve liquid repellency.

o Y^C2

[0255] Y^C2 is a hydrocarbon optionally having a substituent, a hydrocarbon aromatic ring optionally having a substituent or a heterocyclic linker optionally having a substituent.

[0256] Y^C2 may be a hydrocarbon group or a non-hydrocarbon group (including a heteroatom). Y^C2 may be aliphatic or aromatic. Y^C2 may be linear, branched or cyclic.

[0257] Y^C2 is a divalent or higher valent group. Y^C2 may have a valence of, for example, 2 to 4, 2 or 3, or 2.

[0258] Y^C2 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more carbon atoms, and may have 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less carbon atoms.

[0259] Y^C2 is composed of one or more selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms and optionally having a substituent, a divalent to tetravalent hydrocarbon aromatic ring optionally having a substituent, and a divalent to tetravalent heterocyclic ring optionally having a substituent.

[0260] The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a cyclic, branched or linear hydrocarbon group. The divalent to tetravalent aliphatic hydrocarbon group having 1 to 40 carbon atoms may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group. The aliphatic hydrocarbon group having 1 to 40 carbon atoms may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more carbon atoms, and may have 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less carbon atoms. The aliphatic hydrocarbon group may have a valence of 2 or more, 3 or more, or 4, and 4 or less, 3 or less, or 2.

[0261] The aliphatic hydrocarbon group may have a substituent. Examples of substituents include -OR', - N(R')₂, -COOR', and a halogen atom (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the aliphatic hydrocarbon group having a substituent, the amount of carbon atom relative to the carbon atom and the heteroatom may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and is preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0262] Examples of the divalent to tetravalent hydrocarbon aromatic ring include groups obtained by removing 2 to 4 hydrogen atoms from hydrocarbon aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. The number of ring constituting atoms of the hydrocarbon aromatic ring is 3 to 20, 4 to 16, or 5 to 12 and preferably 5 to 12. The valence of the hydrocarbon aromatic ring may be 2 or more, 3 or more, or 4, and may be 4 or less, 3 or less, or 2.

[0263] The hydrocarbon aromatic ring may have a substituent. Examples of substituents include -R', -OR', -N(R')₂, -COOR' and a halogen atom (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may or may not have active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the hydrocarbon aromatic ring having a substituent, the amount of carbon atom relative to the carbon atom and the heteroatom may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and is preferably 75 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.

[0264] The divalent to tetravalent heterocyclic ring may be an aliphatic group or an aromatic group. Examples of the divalent to tetravalent heterocyclic rings include groups obtained by removing 2 to 4 hydrogen atoms from pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, and the like. The number of ring constituting atoms of the heterocyclic ring is 3 to 20, 4 to 16, or 5 to 12 and preferably 5 to 12. The heterocyclic ring may have a valence of 2 or more, 3 or more, or 4, and 4 or less, 3 or less, or 2.

[0265] The heterocyclic ring may have a substituent. Examples of substituents include -R', -OR', -N(R')₂, - COOR' and a halogen atom (wherein R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30, 1 to 20, 1 to 10, or 1 to 4 carbon atoms). The substituent may have or be free of active hydrogen. The number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. In the heterocyclic ring having a substituent, the amount of carbon atom relative to the amount of carbon atom and heteroatom may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, and is for example 65 mol% or more, and may be 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, or 70 mol% or less.

[0266] Examples of Y^C2 include

        -Ali-,

        -Cy-,

        -Ali(-)₂,

        -Cy(-)₂,

        (-)₂Ali-,

        (-)₂Cy-,

        (-)₂Ali(-) 2,

        (-)₂Cy(-) 2,

        -Ali-Cy-,

        -Cy-Ali-,

        -Cy-Ali-Cy-,

and

        -Ali-Cy-Ali-

[wherein Ali is an aliphatic hydrocarbon group having 1 to 20 carbon atoms and Cy is a hydrocarbon aromatic ring or a heterocyclic ring].

[0267] Specific examples of Y^C2 include:

-(CH₂)_p- (p is 1 to 40, 1 to 20, or 1 to 10),

a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond,

a branched hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, and

-(CH₂)_q-Cy-(CH₂)_r- (q and r are each independently 0 to 20, for example, 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring).

(Example of Y^C)

[0268] Examples of Y^C will be described. In the following, R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 30 (for example, 1 to 20, 1 to 10, or 1 to 4) carbon atoms.

[0269] When Y^C is divalent, examples of Y^C include -Y^C1-, - Y^C1-Y^C2-, -Y^C1-Y^C2-Y^C1-, -Y^C1-Y^C2-Y^C1-Y^C2-, -Y^C2-, -Y^C2-Y^C1-, - Y^C2-Y^C1-Y^C2-, and -Y^C2-Y^C1-Y^C2-Y^C1-.

[0270] When Y^C is trivalent, examples of Y^C include -Y^C1(-)₂, -Y^C1-Y^C2 (-)₂, -Y^C1-(Y^C2-)₂, -Y^C1-Y^C2-Y^C1(-)₂, -Y^C1-Y^C2(-Y^C1-)₂, - Y^C1- (Y^C2-Y^C1-)₂, -Y^C1-Y^C2-Y^C1-Y^C2 (-)₂, -Y^C1-Y^C2-Y^C1-(Y^C2-) ₂, -Y^C1-Y^C2-(Y^C1-Y^C2-)₂, -Y^C1-(Y^C2-Y^C1-Y^C2-)₂;
-Y^C2(-)₂, -Y^C2-Y^C1(-)₂, -Y^C2- (Y^C1-)₂, -Y^C2-Y^C1-Y^C2(-)₂, -Y^C2-Y^C1(-Y^C2-)₂, -Y^C2-(Y^C1-Y^C2-)₂, -Y^C2-Y^C1-Y^C2-Y^C1(-)₂, -Y^C2-Y^C1-Y^C2-(Y^C1-)₂, -Y^C2-Y^C1-(Y^C2-Y^C1-)₂, and -Y^C2-(Y^C1-Y^C2-Y^C1-)₂.

[0271] When Y^C is tetravalent, examples of Y^C include - Y^C1(-)₃, -Y^C1-Y^C2(-)₃, -Y^C1-(Y^C2-)₃, -Y^C1-Y^C2-Y^C1(-)₃, -Y^C1-Y^C2(-Y^C1-)₃, -Y^c1-(Y^C2-Y^C1-)₃, -Y^C1-Y^C2-Y^C1-Y^C2(-)₃, -Y^C1-Y^C2-Y^C1-(Y^C2-)₃, -Y^C1-Y^C2-(Y^C1-Y^C2-)₃, -Y^C1-(Y^C2-Y^C1-Y^C2-)₃;
-Y^C2(-)₃, -Y^C2-Y^C1(-)₃, -Y^C2-(Y^C1-)₃, -Y^C2-Y^C1-Y^C2(-)₃, -Y^C2-Y^C1(-Y^C2-)₃, -Y^C2-(Y^C1-Y^C2-)₃, -Y^C2-Y^C1-Y^C2-Y^C1(-)₃, -Y^C2-Y^C1-Y^C2-(Y^C1-)₃, -Y^C2-Y^C1-(Y^C2-Y^C1-)₃, -Y^C2-(Y^C1-Y^C2-Y^C1-)₃; .

[0272] Preferred examples of Y^C include -Y^C1-, -Y^C1-Y^C2-, - Y^C1-Y^C2-Y^C1-, _ycl_yc2 (-)₂,
-Y^C2-, -Y^C2-Y^C1-, -Y^C2-Y^C1-Y^C2-, -Y^C2-Y^C1(-)₂.

(Preferred Example of Y^C)

[0273] Preferably Y^C may be

        -Y^C11-

or

        -Y^C11-Y^C21-Y^C12-

wherein, independently at each occurrence,

Y^C11 is -O- or -NR'-,

Y^C21 is a hydrocarbon group having 1 to 40 carbon atoms and

Y^C12 is -O-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO₂-, - SO₂NR'-, -C(OR')R'-, or -C(OR') (-)₂.

[0274] Y^C11 is a non-hydrocarbon linker, and is a direct bond or divalent or higher valent group.

[0275] Y^C11 may have a molecular weight of 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more, and 2,000 or less, 1,500 or less, 1,000 or less, 750 or less, or 500 or less.

[0276]  Y^C11 may be a direct bond, -C(=O)-, -C(=O)-NR'- or - C(=S)-NR'-.

[0277] Y^C21 is a divalent hydrocarbon linker, and may be a hydrocarbon group having 1 to 40 carbon atoms.

[0278] Y^C21 may have 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, and 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less carbon atoms.

[0279] The hydrocarbon group having 1 to 40 carbon atoms may be cyclic, branched or linear, and may be a saturated or unsaturated (e.g., saturated) aliphatic hydrocarbon group.

[0280] Specific examples of Y^C21 include:

-(CH₂)_p- (p is 1 to 40, 1 to 20, or 1 to 10),

a linear hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms and having an unsaturated bond,

a branched hydrocarbon group having 1 to 40, 1 to 20, or 1 to 10 carbon atoms, and

-(CH₂)_q-Cy-(CH₂)_r- (q and r are each independently 0 to 20, for example, 1 to 10, and Cy is a hydrocarbon aromatic ring or a heterocyclic ring).

[0281]  Y^C12 may be -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR'-, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -SO₂-, -SO₂NR'-, - C(OR')R'-, or -C(OR')(-)₂.

[0282] Y^C12 may include at least an amide group, a urethane group, a urea group, an imide group, a thioamide group, a thiourethane group, a thiourea group, a thioimide group, a sulfone amide group, a sulfone urea group, a sulfone urethane group, or a sulfone imide group. For example, Y^C12 may include -C(=O)-NR'-, -O-C(=O)-NR'-, -NR'-C(=O)-, -NR'-C(=O)-NR'- or -SO₂NR'-. Inclusion of these groups in Y^C12 may improve liquid repellency.

(Z^C)

[0283] Z^C is a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent. The same explanation in the above (Monovalent hydrocarbon group optionally having a substituent) applies.

[Other modifying groups]

[0284] The hydroxy group of polycarboxylic acid may be substituted by a modifying group other than -Y^C-Z^C_n. Examples of modifying groups include an anionic group and/or a cationic group. The anionic group and/or cationic group are as described in [Other modifying groups] in the polyol described above.

[Production Method]

[0285] The modified body of polycarboxylic acid may be produced by reacting a modifying agent including a modifying group (or a precursor structure of the modifying group) with the hydroxy group of polycarboxylic acid.

(Polycarboxylic acid)

[0286] Polycarboxylic acid has two or more carboxyl groups and is a raw material of the modified body of polycarboxylic acid. Polycarboxylic acid has two or more carboxyl groups in the molecule. Polycarboxylic acid may be aliphatic or aromatic, and is preferably aliphatic.

[0287] Polycarboxylic acid may be a low molecular weight compound (having a weight average molecular weight of, for example, less than 1,000 or 500 or less) and/or a high molecular weight compound. Polycarboxylic acid may have a weight average molecular weight of 100 or more, 300 or more, 500 or more, 1,000 or more, 3,000 or more, 5,000 or more, 10,000 or more, 30,000 or more, 100,000 or more, 300,000 or more, or 500,000 or more, and 1,000,000 or less, 7,500,000 or less, 500,000 or less, 3,000,000 or less, 100,000 or less, 75,000 or less, 50,000 or less, 30,000 or less, 10,000 or less, 5,000 or less, 3,000 or less, 2,000 or less, 1,000 or less, or 500 or less.

[0288] Polycarboxylic acid may have 2 or more, 5 or more, 7 or more, 10 or more, 15 or more, 30 or more, 50 or more, or 100 or more carboxyl groups, and 3,000 or less, 1,000 or less, 750 or less, 500 or less, 300 or less, 100 or less, 50 or less, 30 or less, or 20 or less carboxyl groups.

[0289] The carboxyl group equivalent of polycarboxylic acid may be 20 or more, 40 or more, 60 or more, 80 or more, 100 or more, 120 or more, 150 or more, and may be 1,000 or less, 800 or less, 600 or less, 400 or less, 200 or less, 100 or less, or 75 or less. The carboxyl group equivalent of polycarboxylic acid is obtained by dividing the weight average molecular weight of polycarboxylic acid by the number of hydroxyl groups.

[0290] Polycarboxylic acid may be a natural product. The natural product may be a high molecular weight natural product, a low molecular weight natural product, or a derivative thereof. The above natural product also includes a compound converted from microorganisms.

[0291] Polycarboxylic acid may be at least one selected from the group consisting of a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, a polymer of a carboxyl group-containing compound.

[0292] Dicarboxylic acid has two carboxyl groups, and examples thereof include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, malic acid, tartaric acid, aldaric acid and a salt thereof.

[0293] Tricarboxylic acid has three carboxyl groups, and examples thereof include citric acid, tricarballylic acid, t-aconitic acid, trimellitic acid and a salt thereof.

[0294] Tetracarboxylic acid has four carboxyl groups, and examples thereof include pyromellitic acid and a salt thereof.

[0295] The polymer of a carboxyl group-containing compound has five or more carboxyl groups, and examples thereof include alginic acid, gum tragacanth, gum arabic, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyaspartic acid, polyglutamic acid, hyaluronic acid, heparin, xanthan gum, gellan gum, carboxymethyl cellulose alginate, galacturonic acid, mannuronic acid and a salt thereof.

(Modifying agent)

[0296] The modifying agent is preferably a compound which is reactive to polycarboxylic acid and comprises the above monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.

[0297] Examples of modifying agents are as follows:

Epoxy	(CH2OCH)CH2O-Zc
Amine	H2N-ZC
Hydroxy	HO-ZC

[In the formula, Z^C is as described above].

[0298] Z^C in the structure of the above modifying agent may be replaced with any group constituting the modifying group. For example, Z^C may be a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and for example, Z^C may be -Y^C-Z^C_n.

[0299] The modified body of polycarboxylic acid may also be synthesized by reacting polycarboxylic acid and a modifying agent. For example, modified body of polycarboxylic acid may be synthesized by forming an ester bond by reacting a modifying agent, which is an epoxy compound, with the carboxy group of polycarboxylic acid. Conditions of the reaction between polycarboxylic acid and the modifying agent may be suitably designed by a person skilled in the art, including use of a catalyst (e.g., acid catalyst and base catalyst) and use of a condensing agent depending on the intended product.

{Dispersant}

[0300] The repellent in the present disclosure may comprise a dispersant. The dispersant may be at least one selected from an organic dispersant and an inorganic dispersant. The dispersant may be at least one selected from an anionic dispersant, a nonionic dispersant, a cationic dispersant, an amphoteric dispersant and an inorganic dispersant.

[0301] An organic dispersant and an inorganic dispersant may be used as the dispersant, respectively, or an organic dispersant and an inorganic dispersant may be used in combination.

[0302] An organic dispersant may be used as the dispersant. The organic dispersant may be classified into a nonionic dispersant, an anionic dispersant, a cationic dispersant and an amphoteric dispersant. The organic dispersant may mean a surfactant.

[0303] The dispersant may have no fluorine.

[Nonionic dispersant]

[0304] The dispersant may comprise a nonionic dispersant. The nonionic dispersant may be a nonionic surfactant.

[0305] The nonionic dispersant may be of low molecular weight or high molecular weight. The nonionic dispersant may have a molecular weight of 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0306] Examples of nonionic dispersant include ether, ester, ester ether, alkanolamide, polyol and amine oxide.

[0307] The ether is, for example, a compound having an oxyalkylene group (preferably a polyoxyethylene group).

[0308] The ester is, for example, an ester of an alcohol and a fatty acid. The alcohol is, for example, an alcohol which is 1 to 30 hydric (particularly dihydric to decahydric) and has 1 to 50 carbon atoms (particularly 10 to 30 carbon atoms) (for example, an aliphatic alcohol). Examples of the fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0309]  The ester ether is, for example, a compound in which an alkylene oxide (particularly ethylene oxide) is added to an ester of an alcohol and a fatty acid. The alcohol is, for example, an alcohol which is 1 to 30 hydric (particularly dihydric to decahydric) and has 1 to 50 carbon atoms (particularly 3 to 30 carbon atoms) (for example, an aliphatic alcohol). Examples of the fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms.

[0310] The alkanolamide is formed of for example, a fatty acid and an alkanolamine. The alkanolamide may be a monoalkanolamide or a dialkanolamide. Examples of the fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms. The alkanolamine may be an alkanol with 1 to 3 amino groups and 1 to 5 hydroxyl groups, having 2 to 50, particularly 5 to 30 carbon atoms.

[0311] The polyol may be, for example, a dihydric to pentahydric alcohol having 10 to 30 carbon atoms.

[0312] The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).

[0313] The nonionic dispersant is preferably a nonionic dispersant having an oxyalkylene group (preferably a polyoxyethylene group). The alkylene group in the oxyalkylene group preferably has 2 to 10 carbon atoms. The number of oxyalkylene groups in the molecule of the nonionic dispersant is generally preferably 2 to 100.

[0314] The nonionic dispersant is selected from the group consisting of an ether, an ester, an ester ether, an alkanolamide, a polyol, or an amine oxide, and is preferably a nonionic dispersant having an oxyalkylene group.

[0315] The nonionic dispersant may be, for example, an alkylene oxide adduct of a linear and/or branched aliphatic (saturated and/or unsaturated) group, a polyalkylene glycol ester of a linear and/or branched fatty acid (saturated and/or unsaturated), a sorbitan ester of a linear and/or branched fatty acid (saturated and/or unsaturated), a glycerin ester of a linear and/or branched fatty acid (saturated and/or unsaturated), a polyglycerol ester of a linear and/or branched fatty acid (saturated and/or unsaturated), a sucrose ester of a linear and/or branched fatty acid (saturated and/or unsaturated), a polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (random copolymer or block copolymer), and an alkylene oxide adduct of acetylene glycol. Among them, the nonionic dispersant is preferably a dispersant such that the structures of the alkylene oxide addition moiety and polyalkylene glycol moiety are polyoxyethylene (POE) or polyoxypropylene (POP) or POE/POP copolymer (which may be a random or block copolymer, for example.).

[0316] Furthermore, the nonionic dispersant may not include an aromatic group.

[0317] The nonionic dispersant may be the compound represented by the formula:

        R¹O-(CH₂CH₂O)_p-(R²O)_q-R³

[wherein R¹ is an alkyl group having 1 to 22 carbon atoms, an alkenyl group or an acyl group, having 2 to 22 carbon atoms,

R² is each independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 3 to 10),

R³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms,

p is a numeral of 2 or more,

q is 0 or a numeral of 1 or more.].

[0318] R¹ preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. Preferred examples of R¹ include an octyl group, a nonyl group, a trimethylnonyl group, a lauryl group, a tridecyl group, an oleyl group and a stearyl group.

[0319] R² is, for example, a propylene group and a butylene group.

[0320] In the nonionic dispersant, for example, p may be a numeral of 3 or more (for example, 5 to 200) and q may be a numeral of 2 or more (for example, 5 to 200). Namely, -(R²O)_q- may form, for example, a polyoxyalkylene chain.

[0321] The nonionic dispersant may be, for example, a polyoxyethylene alkylene alkyl ether comprising a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center. The hydrophobic oxyalkylene chain includes, for example, an oxypropylene chain, an oxybutylene chain, and a styrene chain. The oxypropylene chain is preferred among them.

[0322] Specific examples of the nonionic dispersants include a condensation product of ethylene oxide with hexylphenol, isooctatylphenol, hexadecanol, oleic acid, an alkane (C₁₂-C₁₆) thiol, a sorbitan monofatty acid (C₇-C₁₉), an alkyl (C₁₂-C₁₈) amine, or the like, and a sorbitan fatty acid ester, a glycerin fatty acid ester, a polyglycerin fatty acid ester, a sucrose fatty acid ester, a propylene glycol fatty acid ester, a polyoxyethylene alkyl ether, a polyoxyethylene polyoxypropylene alkyl ether, a polyoxyethylene glycerin fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, and a lecithin derivative. Examples of nonionic dispersants include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxybutylene alkyl ether, polyoxyethylene polyoxypropylene glycol and polyethyleneimine ethoxylate.

[0323] The proportion of the polyoxyethylene block can be 5 to 80% by weight, for example, 30 to 75% by weight, particularly 40 to 70% by weight, based on a molecular weight of the nonionic dispersant (copolymer).

[0324] The average molecular weight of the nonionic dispersant is generally 300 to 5,000, for example, 500 to 3,000.

[0325] For example, the nonionic dispersant may be used singly or in admixture of two or more. The nonionic dispersant may be a mixture of a compound with an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound with an HLB of 15 or more. More specifically, it is preferable to select the nonionic dispersant from polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene and polyoxypropylene having an HLB of 1 to 18, sorbitan fatty acid ester, glycerol fatty acid ester, polyglycerol fatty acid ester, sucrose fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene glycerol fatty acid ester and polyoxyethylene sorbitan fatty acid ester having an HLB of less than 7.

[Cationic dispersant]

[0326] The dispersant may comprise a cationic dispersant. The cationic dispersant may be a cationic surfactant. The cationic dispersant may be a compound not having an amide group.

[0327] The cationic dispersant may be of low molecular weight (with a molecular weight of 2,000 or less, in particular, 10,000 or less) or of high molecular weight (with a molecular weight of, for example, 2,000 or more). The cationic dispersant may not have an amide group. The cationic dispersant may have a molecular weight of 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0328] The cationic dispersant may be aliphatic or aromatic, and examples thereof include an ammonium salt (e.g., quaternary ammonium salt). The cationic dispersant may be oxyethylene-added ammonium salt. Specific examples thereof include an amine salt dispersant such as alkylamine salt, an amino alcohol fatty acid derivative, a polyamine fatty acid derivative and imidazoline; a quaternary ammonium salt dispersant such as alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, pyridinium salt, alkyl isoquinolinium salt, benzalkonium chloride and benzethonium chloride; and a polymer cationic dispersant such as polyquaternium-1 to 47. Examples of cationic dispersants include alkyl amine salt and quaternary ammonium salt.

[0329] The low molecular weight cationic dispersant may be a compound represented by the formula:

        R²¹-N⁺(-R²²)(-R²³)(-R²⁴)X^-

wherein R²¹, R²², R²³ and R²⁴ are a hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and

X is an anionic group. Specific examples of R²¹, R²², R²³ and -R²⁴ include an alkyl group (e.g., a methyl group, a butyl group, a stearyl group, a palmityl group) and an aromatic group (e.g., a benzyl group, phenyl group). Specific examples of X include a halogen (e.g., chlorine) and an acid (e.g., hydrochloric acid and acetic acid). The cationic dispersant may be monoalkyltrimethylammonium salt (in which alkyl has 4 to 40 carbon atoms) and benzalkonium chloride.

[0330] More specifically, the low molecular weight cationic dispersant may be an ammonium salt represented by the formula:

        R¹_p-N⁺-R²_qX^-

[wherein R¹ is a C12 or higher (e.g., C₁₂ to C₅₀) linear and/or branched aliphatic (saturated and/or unsaturated) group,

R² is H or a C1 to 4 alkyl group, a benzyl group, a polyoxyethylene group (in which the number of oxyethylene groups is for example, 1 (in particular 2, and especially 3) to 50) (particularly preferably CH₃, C₂H₅),

X is a halogen atom (e.g., chlorine) or a C₁ to C₄ fatty acid salt or a C₁ to C₄ sulfonate,

p is 1 or 2, q is 2 or 3 and p + q = 4.]

R¹ may have 12 to 50, and for example 12 to 30 carbon atoms.

[0331] Examples of the low molecular weight cationic dispersants may include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl di(hydropolyoxyethylene) ammonium chloride, benzyldodecyl di(hydropolyoxyethylene) ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.

[0332] The high molecular weight cationic dispersant may be a polymer having a cationic group (for example, an ammonium group, a quaternary ammonium group) (for example, polypolyquaternium-1 to 47). Examples of high molecular weight cationic dispersants include a cationic natural product (in particular, cationic sugar) such as cationic starch, cationic cellulose (e.g., O-(2-hydroxy-3-(trimethylammonio)propyl)hydroxyethyl cellulose chloride), cationic guar gum, cationic xanthan gum and chitosan; a polymer of a cationic group-containing monomer such as aziridine, vinyl imidazole, aminoalkyl methacrylate, N,N,N',N'-tetramethyl-2-butene-1,4-diamine, quaternary dimethyl ammonium ethyl methacrylic acid, diallyldimethylammonium chloride, dimethylaminopropylamine and quaternary vinyl imidazole.

[Anionic dispersant]

[0333] The dispersant may comprise an anionic dispersant. The anionic dispersant may be an anionic surfactant. The dispersant may not include an anionic dispersant.

[0334] The anionic dispersant may be of low molecular weight or high molecular weight. The anionic dispersant may have a molecular weight of 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0335] Examples of the anionic dispersant include an alkyl ether sulfate, an alkyl sulfate, an alkenyl ether sulfate, an alkenyl sulfate, an olefin sulfonate, an alkanesulfonate, a saturated or unsaturated fatty acid salt, an alkyl or alkenyl ether carbonate, an α-sulfone fatty acid salt, a N-acylamino acid dispersant, a phosphate mono- or diester dispersant, and a sulfosuccinic acid ester. Examples of anionic dispersants include a carboxylic acid salt (e.g., fatty acid salt).

[Amphoteric dispersant]

[0336] The dispersant may comprise an amphoteric dispersant. The amphoteric dispersant may be an amphoteric surfactant.

[0337] The amphoteric dispersant may be of low molecular weight or high molecular weight. The amphoteric dispersant may have a molecular weight of 100 or more, 500 or more, 1,000 or more, 2,000 or more, 4,000 or more, or 6,000 or more, and 100,000 or less, 10,000 or less, 7,500 or less, 5,000 or less, 25,000 or less, 750 or less, or 250 or less.

[0338] Examples of the amphoteric dispersants include, for example, alanines, imidazolinium betaines, amidobetaines, and acetic acid betaine, and specific examples of the amphoteric dispersants include, for example, lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine, lauryl dimethylamino acetic acid betaine, and fatty acid amidopropyldimethylaminoacetic acid betaine.

[Inorganic dispersant]

[0339] The dispersant may comprise an inorganic dispersant.

[0340] The inorganic dispersant has an average primary particle size of 5 nm or larger, 30 nm or larger, 100 nm or larger, 1 µm or larger, 10 µm or larger, or 25 µm or larger, and 100 µm or smaller, 50 µm or smaller, 10 µm or smaller, 1 µm or smaller, 500 nm or smaller, or 300 nm or smaller. The average primary particle size may be measured by a microscope, for example, a scanning electron microscope or a transmission electron microscope. The inorganic dispersant may be hydrophilic particles.

[0341] Examples of inorganic dispersants include polyvalent metal phosphate such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate and hydroxyapatite; carbonate such as calcium carbonate and magnesium carbonate; silicate such as calcium metasilicate; sulfate such as calcium sulfate and barium sulfate; and hydroxide such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide.

[Amount of Dispersant]

[0342] The amount of dispersant may be 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.

{Liquid medium}

[0343] The repellent in the present disclosure may comprise a liquid medium. The liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. The repellent may be a dispersion or a solution. The repellent in the present disclosure may include at least water.

[0344] Examples of the organic solvents include esters (for example, esters having 2 to 40 carbon atoms, specifically ethyl acetate and butyl acetate), ketones (for example, ketones having 2 to 40 carbon atoms, specifically methyl ethyl ketone and diisobutyl ketone), alcohols (for example, alcohols having 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (for example, toluene and xylene), petroleum-based solvents (for example, alkanes having 5 to 10 carbon atoms, specifically, naphtha and kerosene). The organic solvent is preferably a water-soluble organic solvent. The water-soluble organic solvent may include a compound having at least one hydroxy group (for example, polyol such as alcohol and glycol solvent, and an ether form of polyol (for example, a monoether form)). These may be used alone, or two or more of them may be used in combination.

[Amount of liquid medium]

[0345] The amount of liquid medium may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1,000 parts by weight or more, and may be 3,000 parts by weight or less, 2,000 parts by weight or less, 1,000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less relative to 1 part by weight of the liquid-repellent compound.

[0346] The amount of water may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1,000 parts by weight or more, and may be 3,000 parts by weight or less, 2,000 parts by weight or less, 1,000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less based on 1 part by weight of the liquid-repellent compound.

[0347] The amount of the organic solvent may be 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, 300 parts by weight or more, 500 parts by weight or more, or 1,000 parts by weight or more, and may be 3,000 parts by weight or less, 2,000 parts by weight or less, 1,000 parts by weight or less, 500 parts by weight or less, 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less relative to 1 part by weight of the liquid-repellent compound.

{Wax}

[0348] The repellent in the present disclosure may include wax. Containing the wax can impart favorable liquid-repellency to a substrate.

[0349] Examples of wax include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (for example, polyethylene wax and polypropylene wax), oxidized polyolefin wax, silicone wax, animal and vegetable wax and mineral wax. Paraffin wax is preferred. Specific examples of compounds constituting wax include n-alkane (such as tricosan, tetracosane, pentacosane, hexacosane, heptacosan, octacosan, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane), n-alkene (such as 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). The number of carbon atom in the compound constituting the wax is preferably 20 to 60, for example 25 to 45. A molecular weight of the wax may be 200 to 2,000, for example, 250 to 1,500 or 300 to 1,000. These may be used singly or in combination of two or more thereof.

[0350] The wax may have a melting point of 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher, preferably 55°C or higher, more preferably 60°C or higher. The melting point of wax is measured according to JIS K 2235-1991.

[Amount of Wax]

[0351] The amount of wax may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid-repellent compound. The amount of wax may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less based on 100 parts by weight of the liquid-repellent compound.

{Silicone}

[0352] The repellent in the present disclosure may include silicone (polyorganosiloxane). Containing the silicone enables providing favorable texture and durability in addition to favorable liquid-repellency.

[0353] As the silicone, a known silicone can be used, and examples of the silicone include a polydimethylsiloxane and modified silicones (for example, amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, and methylhydrogen silicone). For example, the silicone may be silicone wax having waxy properties. These may be used singly or in combination of two or more thereof.

[0354] A weight average molecular weight of the silicone may be 1,000 or more, 10,000 or more, or 50,000 or more, and may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.

[Amount of Silicone]

[0355] The amount of silicone is 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

{Organic Acid}

[0356] The repellent of the present disclosure may contain an organic acid. As the organic acid, a known organic acid can be used. Examples of the organic acid preferably include, for example, a carboxylic acid, a sulfonic acid, and a sulfinic acid, with the carboxylic acid being particularly preferred. Examples of the carboxylic acid include, for example, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, and citric acid, with the formic acid or acetic acid being particularly preferred. In the present disclosure, one type of organic acid may be used, or two or more thereof may be combined for use. For example, formic acid and acetic acid may be combined for use.

[Amount of Organic Acid]

[0357] The amount of organic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. The amount of organic acid may be adjusted so that a pH of the repellent is 3 to 10, for example 5 to 9, particularly 6 to 8. For example, the repellent may be acidic (pH of 7 or less, for example 6 or less).

{Inorganic acid}

[0358] The repellent in the present disclosure may comprise an inorganic acid. As the inorganic acid, a known inorganic acid can be used. Examples of inorganic acids include hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, boric acid, sulfuric acid and phosphoric acid. In the present disclosure, one inorganic acid may be used, or two or more of them may be used in combination. The addition of inorganic acid can improve the stability of the aqueous dispersion.

[Amount of inorganic acid]

[0359] The amount of the inorganic acid may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of the liquid-repellent compound. The amount of the inorganic acid may be adjusted so that the repellent has a pH of 3 to 10, for example, 5 to 9, and in particular, 6 to 8. The repellent may be acidic (may have a pH of 7 or less, for example, 6 or less).

{Curing Agent}

[0360] The repellent of the present disclosure may contain a curing agent (active hydrogen-reactive compound or active hydrogen-containing compound).

[0361] The curing agent (cross-linking agent) in the repellent can effectively cure the repellent. The curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound, which reacts with an active hydrogen or an active hydrogen-reactive group. Examples of the active hydrogen-reactive compound include an isocyanate compound, epoxy compound, chloromethyl group-containing compound, carboxyl group-containing compound, and hydrazide compound. Examples of the active hydrogen-containing compound include a hydroxyl group-containing compound, an amino group-containing compound and a carboxyl group-containing compound, a ketone group-containing compound, a hydrazide compound, and a melamine compound.

[0362] The curing agent may contain an isocyanate compound. The isocyanate compound may be a polyisocyanate compound. The polyisocyanate compound is a compound having two or more isocyanate groups in one molecule. The polyisocyanate compound serves as a cross-linking agent. Examples of the polyisocyanate compound include, for example, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, and derivatives of these polyisocyanates. The isocyanate compound may be a blocked isocyanate compound (for example, a blocked polyisocyanate compound). The blocked isocyanate compound is a compound in which an isocyanate group of an isocyanate compound is masked with a blocking agent to inhibit reaction.

[0363] Examples of the aliphatic polyisocyanates are aliphatic triisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, an aliphatic diisocyanate of 2,6-diisocyanatomethylcaproate, and aliphatic triisocyanates such as lysine ester triisocyanate, 1,4,8-triisocyanateoctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane. These may be used singly or in combination of two or more thereof.

[0364] Examples of the alicyclic polyisocyanates include, for example, an alicyclic diisocyanate and an alicyclic triisocyanate. Specific examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used singly or in combination of two or more thereof.

[0365] Examples of the aromatic-aliphatic polyisocyanate include an aromatic-aliphatic diisocyanate and aromatic-aliphatic triisocyanate. Specific examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethyl xylylene diisocyanate) or a mixture thereof, and 1,3,5-triisocyanatomethylbenzene. These may be used singly or in combination of two or more thereof.

[0366] Examples of the aromatic polyisocyanates include an aromatic diisocyanate, aromatic triisocyanate, and aromatic tetraisocyanate. Specific examples of the aromatic polyisocyanate include, for example, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate, or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate. These may be used singly or in combination of two or more thereof.

[0367] Examples of the derivative of the polyisocyanate include various derivatives such as a dimer, trimer, biuret, allophanate, carbodiimide, urethodione, urethoimine, isocyanurate, and iminooxadiazinedione of the aforementioned polyisocyanate compounds. These may be used singly or in combination of two or more thereof.

[0368] These polyisocyanates can be used singly or in combination of two or more thereof.

[0369] As the polyisocyanate compound, a blocked polyisocyanate compound (blocked isocyanate), which is a compound obtained by blocking isocyanate groups of the polyisocyanate compound with a blocking agent, is preferably used. The blocked polyisocyanate compound is preferably used because it is relatively stable even in solution and can be used in the same solution as solution of the repellent.

[0370] The blocking agent is an agent that blocks free isocyanate groups. The blocked polyisocyanate compound, for example, can be heated 100°C or higher, for example, 130°C or higher to regenerate isocyanate groups, facilitating a reaction with hydroxyl groups. Examples of the blocking agent include, for example, a phenolic compound, lactam-based compound, aliphatic alcohol-based compound, and oxime-based compound. The polyisocyanate compound may be used singly or in combination of two or more thereof.

[0371] The epoxy compound is a compound having an epoxy group. Examples of the epoxy compound include epoxy compounds having a polyoxyalkylene group, such as a polyglycerol polyglycidyl ether and a polypropylene glycol diglycidyl ether; as well as a sorbitol polyglycidyl ether.

[0372] The chloromethyl group-containing compound is a compound having a chloromethyl group. Examples of the chloromethyl group-containing compound include, for example, a chloromethyl polystyrene.

[0373] The carboxyl group-containing compound is a compound having a carboxyl group. Examples of the carboxyl group-containing compound include, for example, a (poly)acrylic acid, and a (poly)methacrylic acid.

[0374] Specific examples of the ketone group-containing compound include, for example, a (poly)diacetone acrylamide, and diacetone alcohol.

[0375] Specific examples of the hydrazide compound include, for example, hydrazine, a carbohydrazide, and adipic acid hydrazide.

[0376] Specific examples of the melamine compound include, for example, a melamine resin and a methyl etherified melamine resin.

[Amount of Curing Agent]

[0377] The amount of the curing agent may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, and 5 parts by weight or less.

{Other Component}

[0378] The repellent may contain a component other than the aforementioned components. Examples of the other components include, for example, polysaccharides, a paper strengthening agent, an agglomerating agent, a yield improver, a coagulant, a binder resin, an anti-slip agent, a sizing agent, a paper strengthening agent, a filler, an antistatic agent, an antiseptic agent, an ultraviolet absorber, an antibacterial agent, a deodorant, and a fragrance. These may be used singly or in combination of two or more thereof.

[0379] In addition to the above components, as other components, for example, other water-repellent and/or oil-repellent agents, a dispersant, a texture modifier, a softening agent, a flame retarder, a coating material fixing agent, a wrinkle-resistant agent, a drying rate adjuster, a cross-linking agent, a film formation agent, a compatibilizer, an antifreezing agent, a viscosity adjuster, an ultraviolet absorber, an antioxidant, a pH adjuster, an insect repellent, an antifoaming agent, an anti-shrinkage agent, a laundry wrinkle-resistant agent, a shape retention agent, a drape retention agent, an ironing improving agent, a brightening agent, a whitening agent, fabric softening clay, a migration-proofing agent such as a polyvinylpyrrolidone, a polymer dispersant, a soil release agent, a scum dispersant, a fluorescent brightening agent such as 4,4-bis(2-sulfostyryl)biphenyldisodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals Plc), a dye fixing agent, an anti-color fading agent such as 1,4-bis(3-aminopropyl)piperazine, a stain removing agent, enzymes such as cellulase, amylase, protease, lipase, and keratinase as fiber surface modifiers, a foam inhibitor, and silk protein powder that can impart texture and functions of silk such as moisture absorption and release properties, and surface modified products or emulsified dispersions thereof (for example, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical Co., Ltd.), hydrolyzed silk liquid (Jomo), SILKGEN G Soluble S (ICHIMARU PHARCOS Co., Ltd.)), an antifouling agent (for example, a nonionic polymer compound composed of an alkylene terephthalate and/or an alkylene isophthalate units and a polyoxyalkylene unit (for example, FR627 manufactured by GOO CHEMICAL CO., LTD.), SRC-1 manufactured by Clariant (Japan), K. K.), can be compounded. These may be used singly or in combination of two or more thereof.

[Amount of Other Component]

[0380] Each amount or the total amount of other components may be 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 75 parts by weight or more, or 100 parts by weight or more, relative to 100 parts by weight of the liquid-repellent compound, and may be 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.

<Method for producing pulp composition/ pulp product>

[0381] The pulp composition of the present disclosure may be obtained by treating a pulp substrate with a repellent containing a liquid-repellent compound.

[0382] A pulp product may be obtained by subjecting the resulting pulp composition to processing such as drying, heating and forming according to need.

[0383] The repellent in the present disclosure can be applied to a pulp substrate as a treatment agent (particularly a surface-treating agent) by a conventionally known method. The treatment method may be a method for dispersing the repellent in the present disclosure in an organic solvent or water, if necessary, to dilute it and allowing it to adhere to an inside of a pulp substrate and/or on a surface thereof and drying by a known method such as dip coating, spray coating, and foam coating. The dilution factor, which may be changed depending on the concentration and the purpose of use of the repellent, may be 3 to 2,000 times, and for example, 10 to 100 times. After drying, a pulp product to which a solid component of the repellent has been adhered, is obtained. If necessary, the repellent of the present disclosure may be applied in combination with a suitable cross-linking agent, and curing may be carried out.

[0384]  The repellent can be applied to a pulp substrate by any of methods known for treating a pulp substrate with liquid. The pulp substrate may be immersed in the repellent, the pulp substrate and the repellent may be mixed, or solution may be adhered or sprayed onto the pulp substrate. The treated pulp substrate is preferably dried and cured by heating in order to develop liquid-repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C, or 100°C to 120°C. In the present disclosure, the heating time may be 5 seconds to 60 minutes, for example, 30 seconds to 3 minutes.

[0385] As the method for treating a pulp substrate, an internal addition treatment method in which repellent is added to a pulp substrate before papermaking (e.g., in the form of pulp slurry), or an external addition treatment method in which repellent is applied to a pulp substrate after papermaking (e.g., a pulp product), can be employed. Examples of internal addition treatment methods include mixing and dipping, and the internal addition treatment method may include a step of adding a repellent to pulp slurry and mixing it with stirring. Examples of external addition treatment methods include spraying, coating, dipping and foam coating and more specifically a pound-type two-roll size press, a gate roll type size press and a rod metering type size press. The treatment may be external addition treatment or internal addition treatment. For example, when the pulp substrate is paper, the repellent may be applied to paper, or solution may be adhered or sprayed onto paper, or the repellent may be mixed with pulp slurry before papermaking to perform treatment. When the pulp substrate is a fiber material, examples of treatment methods include padding treatment, dip treatment, spray treatment, and coating treatment. Examples of padding treatment include the method involving using the padding apparatus as described on pages 396 to 397 of Seni Sensyoku Kako Jiten (in Japanese; Fiber-dyeing process dictionary) (published by THE NIKKAN KOGYO SHIMBUN, LTD., 1963) and pages 256 to 260 of Irozome Kagaku (in Japanese; dyeing chemistry) III (published by Jikkyo Shuppan Co., Ltd., 1975). Examples of the coating treatment include the method involving using a coating machine as described on pages 473 to 477 of Sensyoku Shiage Kiki Soran (in Japanese; Comprehensive guide to dyeing and finishing machines) (published by Fiber Japan CO., LTD., 1981). Examples of the dip treatment include the method involving using a batch type dyeing machine as described on pages 196 to 247 of Sensyoku Shiage Kiki Soran (in Japanese; Comprehensive guide to dyeing and finishing machines) (published by Fiber Japan CO., LTD., 1981), and for example, a jet dyeing machine, air flow dyeing machine, drum dyeing machine, wince dyeing machine, washer dyeing machine, and cheese dyeing machine can be used. Examples of the spray treatment include a method involving using an air spray that nebulizes and sprays a treatment liquid by compressed air, or an air spray by hydraulic pressure nebulization system.

[0386] The method of treatment may be internal addition treatment in which a repellent is added to pulp slurry before papermaking. The internal addition treatment may include, but is not limited to, one or more of a step of adding the repellent to pulp slurry and mixing it with stirring; a step of sucking and dehydrating the pulp composition prepared in the step through a net-like body of predetermined shape and depositing the pulp composition then to form a pulp formed article intermediate; and a step of molding and drying the pulp formed article intermediate by using a heated molding mold to obtain a pulp formed article. After having been lightly dried at room temperature or elevated temperature, the treated paper may be optionally subjected to heat treatment, depending on the nature of the paper. The temperature of the heat treatment may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, particularly 80°C to 180°C. Carrying out the heat treatment in such a temperature range enables exhibiting, for example, excellent oil resistance and water resistance. The pulp substrate which has undergone internal addition treatment may be subjected to external addition treatment to be treated with the repellent, allowing another liquid-repellent compound to be adhered to the surface.

[0387] The treatment method may be an external addition treatment in which repellent is applied to a pulp substrate after papermaking. The size press used in external addition treatment may be classified depending on the coating method as follows. One coating method involves supplying a coating liquid (size liquid) to a nip portion formed by passing paper between two rubber rolls, creating a pool of the coating liquid called a pond, and allowing the paper to pass through this pool to coat both sides of the paper with the size liquid, which is a method employed for a so-called pound-type two-roll size press. Another coating method is a method used for a gate roll type size press in which a size liquid is applied by a surface transfer type, and a rod metering type size press. In the pound-type two-roll size press, the size liquid easily penetrates into an inside of paper, and in the surface transfer type, a size liquid component is likely to stay on a surface of the paper. In the surface transfer type, a coating layer is likely to stay on a surface of paper more than in the pound-type two-roll size press, and the amount of coating layer formed on the surface is more than in the pound-type two-roll size press. In the present disclosure, even in the case of using the former pound-type two-roll size press, performance can be imparted to paper. After having been lightly dried at room temperature or elevated temperature, the paper treated in such a manner is arbitrarily accompanied by heat treatment that can have a temperature range of up to 300°C, for example up to 200°C, and particularly the temperature range of 80°C to 180°C, depending on the nature of the paper, as a result of which excellent oil resistance, water resistance, and the like can be exhibited.

[0388] Specific examples of the paper products include, for example, paper, a paper container, a pulp formed article, a food packaging material, a food container, gypsum liner board base paper, coated base paper, medium-quality paper, a general liner and core, neutral pure white roll paper, a neutral liner, a rust-proof liner, and metal pasted paper, kraft paper, neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper. Preferred examples of pulp products include a food packaging material and a food container, and in particular, a pulp formed article for food contact.

[0389] Embodiments have been described above, but it will be understood that various modifications can be made to embodiments and details without departing from the spirit and the scope of the claims.

Examples

[0390] Hereinafter, the present disclosure will be described in detail with reference to Examples, but the present disclosure is not limited to these Examples.

<Test Method>

[0391] The test procedures are as follows.

[Volume abundance ratio and median diameter (D50) of particle]

[0392] The volume abundance ratio of particles with a size of 100 µm or larger, the volume abundance ratio of particles with a size of 10 µm or larger and the median diameter (D50) of the liquid-repellent compound and the aqueous dispersion were calculated from the volume-based frequency distribution (volume distribution) obtained by the measurement using a laser diffraction/scattering apparatus.

[Preparation Example 1: Preparation of decaglycerol dodecabehenyl ester dispersion]

[0393] 2 g of decaglycerol dodecabehenyl ester (degree of polymerization: 10, hydroxy group substitution ratio: 12/12*100 [100%], biobased ratio: 100%), which was a modified body of polyol, 0.2 g of polyethylene oxide trimethylnonyl ether (HLB: 13) and 17.8 g of water were mixed to give a precursor of water-dispersible repellent A. The precursor of water-dispersible repellent A was heated to 80°C and then stirred by a homogenizer at 7,000 rpm for 20 minutes to give a water-dispersible repellent. The resulting water-dispersible repellent had a volume abundance ratio of particles with a size of 100 µm or larger of 0% and a median diameter D50 of 19.8 um.

[Preparation Example 2: Preparation of ethylene bis(stearic acid amide) dispersion]

[0394] 2 g of N,N'-ethylene bis(stearic acid amide) which had been pulverized by a jet mill (biobased content: 97%, melting point: 143°C, particle size in pulverization: 18 µm), 0.2 g of polyethylene glycol trimethylnonyl ether (HLB: 13) and 17.8 g of water were mixed to give a water-dispersible composition (volume abundance ratio of particles with a size of 100 µm or larger: 3.9%, volume median diameter: 18 um).

[Preparation Example 3: Preparation of ethylene bis(hydroxystearic acid amide) dispersion]

[0395] 2 g of N,N'-ethylene-bis-12-hydroxystearyl amide which had been pulverized by a jet mill (biobased content: 95%, melting point: 145°C, particle size in pulverization: 17 um), 0.2 g of EO/PO polyalkylene glycol natural alcohol ether and 17.8 g of water were mixed to give a water-dispersible composition (volume abundance ratio of particles with a size of 100 µm or larger: 5%, volume median diameter: 17 µm).

[Preparation Example 4: Preparation of ethylene bis(oleic acid amide) dispersion]

[0396] 2 g of N,N'-ethylene-bis(oleic acid amide) which had been pulverized by a jet mill (biobased content: 96%, melting point: 116°C, particle size in pulverization: 24 µm), 0.2 g of EO/PO polyalkylene glycol alcohol ether (HLB: 7) and 17.8 g of water were mixed to give a water-dispersible composition (volume abundance ratio of particles with a size of 100 µm or larger: 0%, volume median diameter: 24 µm).

[Preparation Example 5: Preparation of xylylene bis(hydroxystearic acid amide) dispersion]

[0397] 2 g of N,N-xylylene-bis-12-hydroxystearylamide which had been pulverized by a jet mill (biobased content: 83%, particle size in pulverization: 9 µm), 0.2 g of polyethylene glycol trimethylnonyl ether (HLB: 13) and 17.8 g of water were mixed to give a water-dispersible composition (volume abundance ratio of particles with a size of 100 µm or larger: 0%, volume median diameter: 9 µm).

[Preparation Example 6: Preparation of hexamethylene bis(hydroxystearic acid amide) dispersion]

[0398] 2 g of N,N'-hexamethylene-bis-12-hydroxystearylamide which had been pulverized by a jet mill (biobased content: 85%, melting point: 134°C, particle size in pulverization: 12 µm), 0.2 g of EO/PO polyalkylene glycol natural alcohol ether and 17.8 g of water were mixed to give a water-dispersible composition (volume abundance ratio of particles with a size of 100 µm or larger: 3.5%, volume median diameter: 12 µm).

[Preparation of pulp mold]

[0399] Pulp mold was formed using an automatic mold molding machine. In the lower part thereof, a net-like body was arranged on a pulp mold molding mold made of metal with many suction holes, a metal tank was arranged in the upper part, and a mixture of pulp slurry and the water-dispersible repellent (a pulp composition) was charged in the upper metal tank. From the opposite side of the pulp mold molding mold to the side where the net-like body was arranged, the pulp composition was suctioned and dehydrated through the pulp mold molding mold and the net-like body by a vacuum pump, and solids (pulp, etc.) contained in the pulp composition were allowed to deposit on the net-like body to obtain a pulp mold intermediate. Next, the resulting pulp mold intermediate was dried by applying pressure of 0.05 to 5 MPa thereto from the tops and bottoms of male and female molding molds made of metal, which have been heated to 60 to 250°C. Thus, a pulp mold product formed into the shape of a container was produced.

[Oil-resistance test]

[0400] After pouring 100 ml of corn oil at 65°C into the pulp mold and allowing it to stand at room temperature for 45 minutes, the corn oil was removed from the pulp mold, and the degree of staining in the pulp mold was evaluated. The evaluation scores were set as follows according to the degree of staining.

5: No stains inside the pulp mold.

4: Stains inside the pulp mold. No stains on the backside.

3: Stains the inside the pulp mold. Slight stain bleed out on the backside.

2: Stains inside the pulp mold. The area of stain bleed out to the backside is less than 50% of the total area.

1: Stains inside the pulp mold. The area of stain bleed out to the backside is 50% or more and less than 100% of the total area.

0: Stains over the backside.

<Example 1>

[0401] An aqueous pulp slurry with a concentration of 0.5% by weight containing 25% of bagasse pulp and 75% of wood pulp based on the total amount of pulp was prepared. The decaglycerol dodecabenenyl ester dispersion of Preparation Example 1 was added thereto so that the ratio of the dispersion was 3% by weight in terms of solid content, relative to pulp, to prepare a pulp composition. The pulp composition was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results are shown in Table 1.

<Example 2>

[0402] An aqueous pulp slurry with a concentration of 0.5% by weight containing 100% of bagasse pulp based on the total amount of pulp was prepared. The decaglycerol dodecabenenyl ester dispersion of Preparation Example 1 was added thereto so that the ratio of the dispersion was 3% by weight in terms of solid content, relative to pulp, to prepare a pulp composition. The pulp composition was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results are shown in Table 1.

<Example 3>

[0403] Pulp mold was prepared in the same manner as in Example 1 except for adding 0.45% by weight of AKD (alkyl ketene dimer) based on pulp when the pulp composition was prepared. The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results are shown in Table 1.

<Example 4>

[0404] Pulp mold was prepared in the same manner as in Example 1 except for adding 0.1% by weight of a rosin sizing agent based on pulp when the pulp composition was prepared. The pulp mold prepared was subjected to the oil-resistance test, which scored 4 points. The results are shown in Table 1.

<Example 5>

[0405] An aqueous pulp slurry was prepared in the same manner as in Example 1. The ethylene bis(stearic acid amide) dispersion of Preparation Example 2 was added thereto so that the ratio of the dispersion was 2% by weight in terms of solid content, relative to pulp, to prepare a pulp composition. Pulp mold was prepared and subjected to the oil-resistance test in the same manner, which scored 4 points. The results are shown in Table 1.

<Example 6>

[0406] An aqueous pulp slurry was prepared in the same manner as in Example 1. The ethylene bis(hydroxystearic acid amide) dispersion of Preparation Example 3 was added thereto so that the ratio of the dispersion was 3% by weight in terms of solid content, relative to pulp, to prepare a pulp composition. The pulp composition was charged into an automatic mold molding machine to prepare a pulp mold. Pulp mold was prepared and subjected to the oil-resistance test in the same manner, which scored 4 points. The results are shown in Table 1.

<Example 7>

[0407] An aqueous pulp slurry was prepared in the same manner as in Example 1. The ethylene bis(oleic acid amide) dispersion of Preparation Example 4 was added thereto so that the ratio of the dispersion was 7% by weight in terms of solid content, relative to pulp, to prepare a pulp composition. Pulp mold was prepared and subjected to the oil-resistance test in the same manner, which scored 4 points. The results are shown in Table 1.

<Example 8>

[0408] An aqueous pulp slurry was prepared in the same manner as in Example 1. The xylylene bis(hydroxystearic acid amide) dispersion of Preparation Example 5 was added thereto so that the ratio of the dispersion was 2% by weight in terms of solid content, relative to pulp, to prepare a pulp composition. Pulp mold was prepared and subjected to the oil-resistance test in the same manner, which scored 4 points. The results are shown in Table 1.

<Example 9>

[0409] An aqueous pulp slurry was prepared in the same manner as in Example 1. The hexamethylene bis(hydroxystearic acid amide) dispersion of Preparation Example 6 was added thereto so that the ratio of the dispersion was 3% by weight in terms of solid content, relative to pulp, to prepare a pulp composition. Pulp mold was prepared and subjected to the oil-resistance test in the same manner, which scored 4 points. The results are shown in Table 1.

<Comparative Example 1>

[0410] An aqueous pulp slurry with a concentration of 0.5% by weight containing 100% of wood pulp based on the total amount of pulp was prepared, and pulp mold was prepared in the same manner as in Example 1. The pulp mold prepared was subjected to the oil-resistance test, which scored 3 points. The results are shown in Table 1.

<Comparative Example 2>

[0411] An aqueous pulp slurry with a concentration of 0.5% by weight containing 100% of wood pulp based on the total amount of pulp was prepared, and pulp mold was prepared in the same manner as in Example 7. The pulp mold prepared was subjected to the oil-resistance test, which scored 3 points. The results are shown in Table 1.

<Comparative Example 3>

[0412] An aqueous pulp slurry with a concentration of 0.5% by weight containing 100% of bagasse pulp based on the total amount of pulp was prepared. A sugar fatty acid ester dispersion (SEFOSE 1618U (manufactured by Procter & Gamble Chemicals)) was added thereto so that the ratio of the dispersion was 3% by weight in terms of solid content, relative to pulp, and 0.1% by weight of a polyamine-based resin was added thereto relative to pulp as a combination chemical to prepare a pulp composition. The pulp slurry was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold was subjected to the oil-resistance test, which scored 1 point. The results are shown in Table 1.

<Comparative Example 4>

[0413] An aqueous pulp slurry with a concentration of 0.5% by weight containing 25% of bagasse pulp and 75% of wood pulp based on the total amount of pulp was prepared, and a pulp composition was prepared in the same manner as in Comparative Example 3. Pulp mold was prepared and subjected to the oil-resistance test, which scored 2 points. The results are shown in Table 1.

<Comparative Example 5>

[0414] An aqueous pulp slurry with a concentration of 0.5% by weight containing 25% of bagasse pulp and 75% of wood pulp based on the total amount of pulp was prepared. The pulp slurry was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold prepared was subjected to the oil-resistance test and the water-resistance test, both of which scored 0 points.

<Comparative Example 6>

[0415] An aqueous pulp slurry with a concentration of 0.5% by weight containing 100% of bagasse pulp based on the total amount of pulp was prepared. The pulp slurry was charged into an automatic mold molding machine to prepare a pulp mold. The pulp mold prepared was subjected to the oil-resistance test and the water-resistance test, both of which scored 0 points.

[0416] The results are summarized in the following table.

[Table 1]

	Repellent	Bagasse pulp (%)	Wood pulp (%)	Amount of repellent added (%)	Combinatio n chemical	Oil resista nce
Example 1	Decaglycerol dodecabehenyl ester	25	75	3	-	4
Example 2	Decaglycerol dodecabehenyl ester	100	0	3	-	4
Example 3	Decaglycerol dodecabehenyl ester	25	75	3	AKD	4
Example 4	Decaglycerol dodecabehenyl ester	25	75	3	Rosin sizing agent	4
Example 5	Ethylene bis(stearic acid amide)	25	75	2	-	4
Example 6	Ethylene bis(hydroxystearic acid amide)	25	75	3	-	4
Example 7	Ethylene bis(oleic acid amide)	25	75	7	-	4
Example 8	Xylylene bis(hydroxystearic acid amide)	25	75	2	-	4
Example 9	Hexamethylene bis(hydroxystearic acid amide)	25	75	3	-	4
Comparative Example 1	Decaglycerol dodecabehenyl ester	0	100	3	-	3
Comparative Example 2	Ethylene bis(oleic acid amide)	0	100	7	-	3
Comparative Example 3	Sugar fatty acid ester (SEFOSE)	100	0	10	Polyamine-based resin	1
Comparative Example 4	Sugar fatty acid ester (SEFOSE)	25	75	10	Polyamine-based resin	2
Comparative Example 5	-	25	75	0	-	0
Comparative Example 6	-	100	0	0	-	0

Claims

1. A pulp composition comprising a liquid-repellent compound and a pulp substrate, wherein

the liquid-repellent compound is a compound having a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and is not a fatty acid ester having a glycoside bond, and

the pulp substrate comprises bagasse pulp.

2. The pulp composition according to claim 1, wherein the liquid-repellent compound has at least one group selected from the group consisting of:

        -OC(=O)R, -COOR, -NHCOR and -CONHR,

wherein R is each independently a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.

3. The pulp composition according to claim 1 or 2, wherein the liquid-repellent compound is a compound formed by modifying amine, polyol or polycarboxylic acid with a hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.

4. The pulp composition according to any one of claims 1 to 3, wherein an amount of the liquid-repellent compound is 0.5% by weight or more and 25% by weight or less based on the pulp substrate.

5. The pulp composition according to any one of claims 1 to 4, wherein an amount of the bagasse pulp is 20% by weight or more and 100% by weight or less in the pulp substrate.

6. The pulp composition according to any one of claims 1 to 5, wherein the pulp composition comprises a dispersant.

7. The pulp composition according to any one of claims 1 to 6, wherein the pulp composition comprises a combination chemical for paper.

8. The pulp composition according to any one of claims 1 to 7, wherein the pulp composition comprises a sizing agent.

9. The pulp composition according to any one of claims 1 to 8, wherein the pulp composition comprises aluminum sulfate.

10. A pulp formed article formed from the pulp composition according to any one of claims 1 to 9.

11. The pulp formed article according to claim 10, which is for food contact.

12. A method for producing a pulp composition, comprising treating a pulp substrate with a repellent comprising a liquid repellent compound, wherein

the liquid-repellent compound is a compound having a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent, and is not a fatty acid ester having a glycoside bond, and

the pulp substrate comprises bagasse pulp.

13. The method for producing a pulp composition according to claim 12, wherein the liquid-repellent compound has at least one group selected from the group consisting of:

        -OC(=O)R, -COOR, -NHCOR and -CONHR,

wherein R is each independently a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms and optionally having a substituent.