MACHINE DISHWASH DETERGENT COMPOSITION

Description

Technical field of the invention

[0001] The present invention is in the field of a machine dishwash detergent composition comprising an amino (poly)carboxylic compound such as methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA) and imino disuccinic acid (IDS), and at least two different nonionic surfactants.

Background to the invention

[0002] Machine dishwash detergent (MDW) compositions comprising a builder and a mixture of surfactants are known in the art. In WO98/11190 a detergent composition is described comprising a phosphate or citrate based builder and a mixed surfactant system. The surfactant system contains a nonionic surfactant having a high cloud point, and a zwitterionic surfactant. Such systems have the disadvantage that these can cause serious foaming in the dishwashing machine, so that the use of these is limited. WO00/50552 describes machine dishwash detergent compositions containing a builder, and a surfactant system of an oxide surfactant and a low foaming surfactant chosen from a specific group of surfactants, for stain removal and in particular reduction of red sauce.
In US 20070219110 phosphate free automatic dishwashing compositions comprising MGDA, non-ionic surfactant and a bleach are described showing good cleaning results.
In WO9505440 phosphate free automatic dishwashing compositions for removal of grease are described which contain specific alkyl dimethyl amine oxides.

[0003] DE102005060431 describe machine dishwashing compositions showing good cleaning and rinsing results, and comprising a polymer having at least a positively charge, ethoxylated alcohol and MGDA. Phosphorous based builders, such as phosphates, have been used for many years in a wide variety of detergent compositions. However, as part of an increasing trend towards environmentally friendly detergent compositions, alternative building agents have been developed and these alternative builders have found their way into commercial detergent products. Glutamic-N,N-diacetate (GLDA), methyl-glycine diacetate (MGDA), imino disuccinic acid (IDS) and citrate are examples of environmentally friendly builders that are used in commercial detergent products. Unfortunately, in use in machine dish detergents, amino (poly)carboxylates have the disadvantage of a reduced wash performance compared to phosphate. In particular the level of degreasing and grease build-up prevention was found to be less than for phosphate based compositions.
In EP 1741774, machine dishwash detergent compositions are described that can contain a phosphate free builder, a low foaming nonionic surfactant, a bleach and a bleach catalyst.

Summary of the invention

[0004] The current invention provides for a phosphate-free machine dishwash detergent composition which provides a combination of improved cleaning and/or degreasing, whilst maintaining spotting and filming performance. Also, the disadvantages connected with the systems described above are reduced or no longer present.

[0005] In one embodiment, the invention thereto provides a phosphate free machine dishwash detergent composition comprising

a) 15 - 70 wt% of a non-phosphate containing builder system comprising at least one of MGDA, GLDA and IDS, and preferably 20-60 wt.% of such a builder system, and more preferred 25-60 wt.% of such a builder system;

b) 0.1-15 wt.% of a nonionic surfactant system comprising

i) a C₁₀-C₁₈ alkyl dimethylamine oxide,

ii) an alkylpolyethylene glycol ether nonionic surfactant of the formula R¹ - (EO)_x OH, wherein R¹ is a linear or branched alkyl group containing between 10 to about 18 carbon atoms and x is an integer between 20 and 180, preferably between 25 and 120,

iii) optionally, an alkylpolyethylene glycol ether nonionic surfactant of the formula R² - (EO)_x OH, wherein R² is a linear or branched alkyl group containing between 10 to 18 carbon atoms and preferably between 11-15, and x is between 5 and 12, preferably between 6 and 10,

iv) optionally, a further nonionic surfactant different from i), ii), or iii);

wherein the weight amount of the C₁₀-C₁₈ alkyl dimethylamine oxide is in the range of 2.5-30 wt.% of the total weight amount of the non-ionic surfactant system present;

c) at least one of a bleaching agent or enzymes.

Further improved cleaning benefits have been found when the above composition comprises an oxygen bleach and also a manganese complex bleach catalyst. The presence of a catalyst containing manganese was found to provide a significant improvement in cleaning, in particular in the removal of stains such as tea stains. Cleaning benefits are furthermore obtained when a bleach precursor is present in the composition. Accordingly, in its second embodiment, the invention concerns a phosphate-free machine dishwash detergent composition as set forth in claim 1, wherein the composition further comprises a bleaching agent and a manganese complex bleach catalyst.
In a further embodiment, a phosphate-free machine dishwash detergent composition is proposed comprising

a) 15 - 70 wt.% of a non-phosphate containing builder system comprising at least one of MGDA, GLDA and IDS, wherein at least 30 wt.% of the non-phosphate builder system (wt.% based on total weight of the builder system) is an amino (poly)carboxylic compound selected from MGDA, GLDA and/or IDS,

b) 0.1-15 wt.% of a nonionic surfactant system as indicated above,

c) a bleaching agent and

d) a manganese complex bleach catalyst.

Definitions

[0006] Weight percentages (indicated as 'wt.%') herein are calculated based upon total weight of the composition, unless indicated otherwise.

[0007] Whenever an amount or concentration of a component is quantified herein, unless indicated otherwise, the quantified amount or quantified concentration relates to said component per se, even though it may be common practice to add such a component in the form of a solution or of a blend with one or more other ingredients.

[0008] In the context of this invention, 'substantially free of' means a maximum concentration of the compound concerned of 1 wt.% based on the total weight of the detergent composition. Phosphate free in the context of this invention means that no phosphate is added in the preparation of the detergent composition.

[0009] At the instances in this specification where reference is made to amino (poly)carboxylic acids the corresponding salts are meant to be included as well.

[0010] The amounts mentioned in this specification are based on the recommended amount of detergent composition used per main wash cycle. Machine dishwash detergent compositions according to the invention may suitably be dosed in the wash liquor at levels of from 2 g/l to 10 g/l.

[0011] The invention is in particular suitable for multifunctional machine dishwash detergent compositions.
However, also benefits can be achieved by applying the invention to a detergent composition in which a separate rinse aid is used in the final steps of the dishwashing process.
In a preferred embodiment the detergent composition is a multifunctional machine dishwash composition.

Detailed description of the invention

Builder

[0012] In the compositions of the current invention at least 15 wt.% of a non-phosphate builder system is present. The compositions of the invention will contain one or more amino (poly)carboxylic compounds selected from methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA) and imino disuccinic acid (IDS) or combinations thereof. These compounds act as builders, and bind ions like magnesium and calcium.
The most preferred type of amino polycarboxylic compound for solid compositions is MGDA, whereas where liquid or gel-like compositions are envisaged, GLDA is the preferred amino polycarboxylic compound used.
Optionally the builder system in the composition comprises a further builder which may for example be selected from the group comprising alkali metal carbonates, bicarbonates and citric acid.

[0013] It is preferred that at least 30 wt.% of the non-phosphate builder system (wt.% based on total weight of the builder system) is an amino (poly)carboxylic compound selected from MGDA, GLDA and/or IDS, and further preferred at least 45 wt.%. Where at least 50 wt.%, and up to 100 wt.% of the builder system is chosen from MGDA, GLDA, IDS or any combination thereof, the result of improvement was found to be even more pronounced.
The phosphate-free machine dishwash detergent composition of the invention preferably contains a non-phosphate builder system in amounts between 20 and 60 wt.%, more preferred between 25 and 60 wt.%, and most preferred between 30 and 45 wt.%. Where the composition of the invention contains an amount of about 30, 35 or 40 wt% of at least one (poly)carboxylic compound from the group of MGDA, GLDA and IDS, this was found to lead to good results on all aspects in the detergent composition of the current invention. MGDA and GLDA or combinations thereof are preferred.

[0014] The form in which the MGDA and/or GLDA and/or IDS and/or their salts can be applied in the compositions can be any, such as a powder or a granule or a solution, and is suitably chosen depending in the format of the detergent composition foreseen.

Surfactant

[0015] The nonionic surfactant system is present in an amount of 0.1 up to 15% by weight, and preferably present in an amount of 0.5 up to 10% by weight, further preferred up to 0.5-8 wt.%. Even further preferred is 0.5-7 wt.%, the range of 2-7 wt.% is most preferred.

[0016] Good cleaning and improved degreasing while also obtaining optimal handling is found when 0.05-2 wt.% and preferably 0.1-1.8 wt.%, further preferred 0.2-1 wt.%, of the group of C₁₀-C₁₈ alkyl dimethylamine oxides is present in the composition.

[0017] The C₁₀-C₁₈ alkyl dimethylamine oxides of the present invention contain are nonionic surfactants.

[0018] A preferred embodiment is found for compositions wherein the detergent composition of the present invention comprises a nonionic surfactant mixture as defined in claim 1 wherein the amount of C₁₀-C₁₈ alkyl dimethylamine oxides present is in the range of 2.5-25 wt.% of the total amount of nonionic surfactants present in the composition, and preferably is in the range of 5-20 wt.% of the total amount of the surfactant system, and most preferred in the range of 7.5-15 wt.%.

[0019] In particular, a C₁₄-C₁₈ alkyl dimethylamine oxide is preferred as the amine oxide of formula i). For example, Empigen™ OD (supplied by Huntsman) is a suitable amine oxide for use in the present invention.
The amine oxides of this formula are often sold as a solution. In this specification, the weight amount of the amine oxide indicated is the amount of amine oxide which is present in such solution.

[0020] The composition should comprise an alkylpolyethylene glycol ether nonionic surfactant of the formula R¹ - (EO)_x OH, wherein R¹ is a linear or branched alkyl group containing between 10 to about 18 carbon atoms and x is an integer between 20 and 180, preferably between 25 and 120. Examples of such non-end capped ethoxylated glycol ether are found in the Lutensol™ AT series, supplied by BASF.
These alkylpolyethylene glycol ethers surfactants are preferably present in an amount of 1.2-6 wt.% of the total detergent composition, and preferably in an amount of 2-5 wt.%, and further preferred 2.5-5 wt.%.

[0021] Optionally, a third nonionic surfactant is present, said third surfactant being an alkylpolyethylene glycol ether nonionic surfactant of the formula R² - (EO)_x OH, wherein R² is a linear or branched alkyl group containing between 10 to about 18 carbon atoms and preferably between 11-15 carbon atoms, and x is between 5 and 12, and preferably between 6 and 10. Examples of such surfactants can be found in the Lutensol™ TO series of BASF, which are alkylpolyethylene glycol ethers made, for example those made from a saturated iso-C₁₃ alcohol, such as Lutensol™ TO7. Suitably, surfactants of this formula are present in an amount of 0.1-12 wt.%, preferably 1-10 wt.%, further preferred 1-8 wt.%, and most preferred 2-6 wt.%.

[0022] In a preferred embodiment of the invention, the detergent composition comprises 1.5-15 wt.%, of a surfactant system which contains

i) 0.05 - 2 wt.% of a C₁₀-C₁₈ alkyl dimethylamine oxide,

ii) 1.2 - 6 wt.% of an alkylpolyethylene glycol ether nonionic surfactant of the formula R¹- (EO)_x OH, wherein R¹ is a linear or branched alkyl group containing between 10 to about 18 carbon atoms and x is an integer between 20 and 180, preferably between 25 and 120,

iii) 0.1 - 12 wt.% of an alkylpolyethylene glycol ether nonionic surfactant of the formula R²-(EO)_xOH, wherein R² is a linear or branched alkyl group containing between 10 to about 18 carbon atoms and preferably between 11-15 carbon atoms, and x is between 5 and 12, preferably between 6 and 10,

iv) and optionally, a further nonionic surfactant different from any of the nonionics of formula i), ii), or iii).

[0023] A further preferred surfactant system in this invention comprises 2-10 wt.% of a nonionic surfactant system which contains

i) 0.1 - 1 wt.% of a C₁₀-C₁₈ alkyl dimethylamine oxide,

ii) 2 - 5 wt.% of an alkylpolyethylene glycol ether nonionic surfactant of the formula R¹-(EO)_xOH, wherein R¹ is a linear or branched alkyl group containing between 10 to about 18 carbon atoms and x is an integer between 20 and 180, preferably between 25 and 120,

iii) 0.5 - 5 wt.% of an alkylpolyethylene glycol ether nonionic surfactant of the formula R²-(EO)_xOH, wherein R² is a linear or branched alkyl group containing between 10 to about 18 carbon atoms and preferably between 11-15 carbon atoms, and x is between 5 and 12, preferably between 6 and 10,

iv) and optionally, a further nonionic surfactant different from any of the nonionics of formula i), ii), or iii).

[0024] Particular good results with respect to cleaning, degreasing, prevention of spotting and filming, and low foaming during the wash can be obtained when in this detergent composition The weight amount of the C₁₀-C₁₈ alkyl dimethylamine oxide is in the range of 10-25 wt.% of the total weight amount of the surfactant system.

[0025] In addition to the non-end capped ethoxylated glycol ethers and amine oxides indicated above, further nonionic surfactants can be present. It has been found that a further improvement of performance benefits can be obtained when the composition of invention furthermore contains a nonionic surfactant of the formula R³-(PO)_x(EO)_y-CH₂CH (OH) - R⁴; wherein R³ is C₆ - C₁₅; R⁴ is C₄ - C₁₀, and x is an integer in the range of 0 - 10, and y is an integer in the range of 3 - 30. Suitable nonionics to apply in the composition of the invention include modified fatty alcohol polyglycolethers available as Dehypon^R 3697 GRA or Dehypon^R Wet from BASF.

[0026] If an anionic surfactant is used, the total amount thereof present preferably is less than 5 wt.%, and more preferably not more than 2 wt.%, and most preferred less than 1 wt.%. Furthermore, if an anionic surfactant is present, it is preferred that an antifoam agent to suppress foaming is present. Examples of suitable anionic surfactants are methylester sulphonates or sodium lauryl sulphate.

Bleach

[0027] The present composition suitably comprises a bleach compound, which can be a chlorine-, or bromine-releasing agent or a peroxygen compound. Preferably, the bleach compound is a peroxygen compound selected from hydrogen peroxide, hydrogen peroxide-liberating compounds, hydrogen peroxide-generating compounds, as well as the organic and inorganic peroxyacids and water-soluble salts thereof, and mixtures thereof.

[0028] Examples of peroxides and corresponding salts include monopersulphate, perborate monohydrate, perborate tetrahydrate, and percarbonate. Percarbonate is highly preferred.

[0029] The total amount of peroxygen bleach compound(s) is preferably from 5% to 25%, more preferably from 10% to 20% by weight of the composition.

[0030] Organic peracids useful herein include alkyl peroxy acids and aryl peroxyacids such as peroxybenzoic acid and ring-substituted peroxybenzoic acids (e.g. peroxy-alpha-naphthoic acid), aliphatic and substituted aliphatic monoperoxy acids (e.g. peroxylauric acid and peroxystearic acid), and phthaloyl amido peroxy caproic acid (PAP).

[0031] Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as 1,12-di-peroxy-dodecanedioic acid (DPDA), 1,9-diperoxyazelaic acid, diperoxybrassylic acid, diperoxysebacic acid and diperoxy-isophthalic acid, and 2-decyldiperoxybutane-1,4-dioic acid.

[0032] These bleaching agents may be utilised alone or in conjunction with a peroxyacid bleach activator.

Bleach activator

[0033] The detergent composition may contain one or more bleach activators such as peroxyacid bleach precursors. Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named N,N,N',N'-tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4,751,015.

Bleach catalyst

[0034] If desirable, a bleach catalyst, such as a manganese complex, e.g. Mn-Me TACN, as described in EP-A-0458397, or the sulphonimines of US-A-5,041,232 and US-A-5,047,163, can be incorporated.
This bleach catalyst may suitably be present in the composition in the form of an encapsulate, notably an encapsulate that is separate from the bleach particles (to avoid premature bleach activation). The presence of such a manganese complex catalyst can significantly improve the cleaning performance of the detergent composition of the invention and is therefore highly preferred. The presence thereof, in combination with a bleaching agent such as percarbonate, is a preferred embodiment for the current invention.

Enzymes

[0035] As an alternative to the presence of a bleaching agent, enzymes can be present in the composition if the invention. It is preferred that both a bleaching agent and enzymes are present. Examples of enzymes suitable for use in the cleaning compositions of this invention include lipases, cellulases, peroxidases, proteases (proteolytic enzymes), amylases (amylolytic enzymes) and others which degrade, alter or facilitate the degradation or alteration of biochemical soils and stains encountered in cleansing situations so as to remove more easily the soil or stain from the object being washed to make the soil or stain more removable in a subsequent cleansing step. Both degradation and alteration can improve soil removal.

[0036] Well-known and preferred examples of these enzymes are proteases, amylases, cellulases, peroxidases, mannanases, pectate lyases and lipases and combinations thereof. The enzymes most commonly used in detergent compositions are proteolytic and amylolytic enzymes.
Enzymes may be added in liquid or in encapsulated form. In a preferred embodiment of this invention the enzymes are present in encapsulated form. Well know enzyme stabilizers such as polyalcohols/borax, calcium, formate or protease inhibitors like 4-formylphenyl boronic acid may also be present in the composition The proteolytic enzymes in this invention include metalloproteases and serine proteases, including neutral or alkaline microbial serine protease, such as subtilisins (EC 3.4.21.62). The proteolytic enzymes for use in the present invention can be those derived from bacteria of fungi. Chemically or genetically modified mutants (variants) are included. Preferred proteolytic enzymes are those derived from Bacillus, such as B. lentus, B. gibsonii, B. subtilis, B. licheniformis, B. alkalophilus, B. amyloliquefaciens and Bacillus pumilus, of which B. lentus and B. gibsonii are most preferred. Examples of such proteolytic enzymes are Excellase™, Properase™, Purafect™, Purafect™ Prime, Purafect™ Ox by Genencor/DUPONT; and those sold under the trade names Blaze™, Ovozyme™, Savinase™, Alcalase™, Everlase™, Esperase™, Relase™, Polarzyme™, Liquinase™ and Coronase™ by Novozymes.

[0037] Preferred levels of protease in the present composition are from 0.1 to 10, more preferably from 0.2 to 5, most preferably 0.4 to about 4 mg active protease per gram of composition.

[0038] The amylolytic enzymes for use in the present invention can be those derived from bacteria or fungi. Chemically or genetically modified mutants (variants) are included. Preferred amylolytic enzyme is an alpha-amylase derived from a strain of Bacillus, such as B. subtilis, B. licheniformis, B.. amyloliquefaciens or B. stearothermophilus. Examples of such amylolytic enzymes are produced and distributed under the trade name of Stainzyme™, Stainzyme™ Plus, Termamyl™, Natalase™ and Duramyl™ by Novozymes; as well as Powerase™, Purastar™, Purastar™ Oxam by Genencor/DUPONT. Stainzyme™, Stainzyme™ Plus and Powerase™ are the preferred amylases.

[0039] Preferred levels of amylase in the present composition are from 0.01 to 5, more preferably from 0.02 to 2, most preferably from 0.05 to about 1 mg active amylase per gram of composition.

[0040] The enzymes may suitably be incorporated in the detergent composition in liquid or in encapsulated form. In case the composition has a pH of 9.0 and more it is preferred to employ enzymes in encapsulated form.

[0041] Examples of encapsulated forms are enzyme granule types D, E and HS by Genencor/DUPONT and granule types T, GT, TXT and Evity™ of Novozymes.

Buffering Agent

[0042] Buffering agents may be used in compositions according to the present invention in order to adjust and to maintain the alkalinity and pH at the desired level. These are for example, the alkali metal carbonates and bicarbonates, sometimes also borates, and silicates.

Silicates

[0043] Silicates may be added to the formulation. Silicates can act as builder, buffering agent or article care agent. Preferred silicates are sodium silicate such as sodium disilicate, sodium metasilicate and crystalline phyllosilicates and mixtures thereof. The sodium silicates used preferably have Na₂0:Si0₂ ratios of from about 2:1 to 1:4. Silicates are preferably used in the detergent composition in a concentration of 1 to 20%, more preferably of 2 to 10% by weight of the composition.

Dispersing polymers

[0044] In a preferred embodiment of the current invention, the detergent composition furthermore comprises at least one dispersing polymer. Dispersing polymers as referred to in this invention are chosen from the group of anti-spotting agents and/or anti-scaling agents.

[0045] Examples of suitable anti-spotting polymeric agents include hydrophobically modified polycarboxylic acids such as Acusol™ 460 ND (ex Dow) and Alcosperse™ 747 by AkzoNobel, whereas also synthetic clays, and preferably those synthetic clays which have a high surface area are very useful to prevent spots, in particular those formed where soil and dispersed remnants are present at places where the water collects on the glass and spots formed when the water subsequently evaporates.

[0046] Examples of suitable anti-scaling agents include organic phosphonates, amino carboxylates, polyfunctionally-substituted compounds, and mixtures thereof. Particularly preferred anti-scaling agents are organic phosphonates such as

-hydroxy-2 phenyl ethyl diphosphonate, ethylene diphosphonate, hydroxy 1,1-hexylidene, vinylidene 1,1-diphosphonate, 1,2-dihydroxyethane 1,1-diphosphonate and hydroxy-ethylene 1,1-diphosphonate. Most preferred is hydroxy-ethylene 1,1-diphosphonate (EDHP) and 2-phosphono-butane, 1,2,4-tricarboxylic acid (Bayhibit ex Bayer).
Suitable anti-scaling agents are water soluble dispersing polymers prepared from an allyloxybenzenesulfonic acid monomer, a methallyl sulfonic acid monomer, a copolymerizable nonionic monomer and a copolymerizable olefinically unsaturated carboxylic acid monomer as described in US 5 547 612 or known as acrylic sulphonated polymers as described in EP 851 022. Polymers of this type include polyacrylate with methyl methacrylate, sodium methallyl sulphonate and sulphophenol methallyl ether such as Alcosperse™ 240 supplied (AkzoNobel). Also suitable is a terpolymer containing polyacrylate with 2-acrylamido-2 methylpropane sulphonic acid such as Acumer 3100 supplied by Dow. As an alternative, polymers and co-polymers of acrylic acid having a molecular weight between 500 and 20,000 can also be used, such as homo-polymeric polycarboxylic acid compounds with acrylic acid as the monomeric unit. The average weight of such homo-polymers in the acid form preferably ranges from 1,000 to 100,000 particularly from 3,000 to 10,000 e.g. Sokolan™ PA 25 from BASF or Acusol™ 425 from Dow.

[0047] Also suitable are polycarboxylates co-polymers derived from monomers of acrylic acid and maleic acid, such as CP 5 from BASF. The average molecular weight of these polymers in the acid form preferably ranges from 4,000 to 70,000. Modified polycarboxylates like Sokalan™ CP42, Sokalan™ CP50 from BASF or Alcoguard™ 4160 from AkzoNobel may also be used.

[0048] Mixture of anti-scaling agents may also be used. Particularly useful is a mixture of organic phosphonates and polymers of acrylic acid.

[0049] It is preferred that the level of dispersing polymers ranges from 0.2 to 10 wt.% of the total composition, preferably from 0.5 to 8 wt.%, and further preferred from 1 to 6 wt.%.

Optional Other Ingredients

[0050] Glass corrosion inhibitors can prevent the irreversible corrosion and iridescence of glass surfaces in machine dishwash detergents. The claimed composition may suitably contain glass corrosion inhibitors. Suitable glass corrosion agents can be selected from the group consisting of salts of zinc, bismuth, aluminum, tin, magnesium, calcium, strontium, titanium, zirconium, manganese, lanthanum, mixtures thereof and precursors thereof. Most preferred are salts of bismuth, magnesium or zinc or combinations thereof. Preferred levels of glass corrosion inhibitors in the present composition are 0.01-2 wt.%, more preferably 0.01-0.5 wt.%.

[0051] Anti-tarnishing agents may prevent or reduce the tarnishing, corrosion or oxidation of metals such as silver, copper, aluminium and stainless steel. Anti-tarnishing agents such as benzotriazole or bis-benzotriazole and substituted derivatives thereof and those described in EP 723 577 (Unilever) may also be included in the composition. Other anti-tarnishing agents that may be included in the detergent composition are mentioned in WO 94/26860 and WO 94/26859. Suitable redox active agents are for example complexes chosen from the group of cerium, cobalt, hafnium, gallium, manganese, titanium, vanadium, zinc or zirconium, in which the metal are in the oxidation state of II, II, IV V or VI.

[0052] Optionally other components may be added to the formulation such as perfume, colorant or preservatives.

Format

[0053] Compositions of the present invention may be in any suitable physical form, for example powdered and/or granular compositions, pearls, tablets, liquids, gels, or combinations thereof. For the convenience of the consumer, the detergent may be, and preferably is a unit dose, such as a tablet or a single dose pouch or sachet containing the detergent. These can be a single or multi-compartment pouch or sachet.
In a particular embodiment of the invention, at least part of the composition is in the form of the liquid or gel, and the composition comprises 15 - 70 wt% of a non-phosphate containing builder system comprising GLDA.

[0054] Machine dishwash detergent compositions according to the invention may suitably be dosed at levels of 5 to 40 grams per wash, more preferably at 10 to 30 grams per wash.

[0055] Preferably, the machine dishwashing composition is a mildly alkaline product having a solution pH below 12, e.g. from 7-12, preferably from 9-11. The solution pH as meant here is the pH as determined from a solution of 3 g/l of the compositions in distilled water at 20°C.

Claims

1. A phosphate-free machine dishwash detergent composition comprising

a) 15 - 70 wt% of a non-phosphate containing builder system comprising at least one of methylglycine diacetic acid (MGDA), glutamic diacetic acid (GLDA) and imino disuccinic acid (IDS), and prefarably 20-60 wt.% of such a builder system, and more preferred 25-60 wt.% of such a builder system;

b) 0.1-15 wt.% of a nonionic surfactant system comprising

i) a C₁₀-C₁₈ alkyl dimethylamine oxide,

ii) an alkylpolyethylene glycol ether nonionic surfactant of the formula R¹-(EO)_xOH, wherein R¹ is a linear or branched alkyl group containing between 10 to 18 carbon atoms and x is an integer between 20 and 180, preferably between 25 and 120,

iii) optionally, an alkylpolyethylene glycol ether nonionic surfactant of the formula R² - (EO)_x OH, wherein R² is a linear or branched alkyl group containing between 10 to 18 carbon atoms and preferably between 11-15, and x is between 5 and 12, preferably between 6 and 10,

iv) optionally, a further nonionic surfactant different from i), ii), or iii);

wherein the weight amount of the C₁₀-C₁₈ alkyl dimethylamine oxide is in the range of 2.5-30 wt.% of the total weight amount of the non-ionic surfactant system present;

c) at least one of a bleaching agent or enzymes.

2. A phosphate-free machine dishwash detergent composition according to claim 1, wherein the composition comprises a bleaching agent and a manganese complex bleach catalyst.

3. A phosphate-free machine dishwash detergent composition according to any one of claims 1 or 2, wherein at least 30 wt.% of the non-phosphate builder system (wt.% based on total weight of the builder system) is an amino (poly)carboxylic compound selected from MGDA, GLDA and/or IDS.

4. A phosphate-free machine dishwash detergent composition according to any one of the preceeding claims, characterized in that the composition comprises 0.05-2 wt.% of the group of C₁₀-C₁₈ alkyl dimethylamine oxide nonionic surfactant.

5. A phosphate-free machine dishwash detergent composition according to any one of the preceeding claims, characterized in that the C₁₀-C₁₈ alkyl dimethylamine oxide is chosen from the group of C₁₄-C₁₈ alkyl dimethylamine oxide.

6. A phosphate-free machine dishwash detergent composition according to any one of the preceeding claims, characterized in that the amount of C₁₀-C₁₈ alkyl dimethylamine oxides present is in the range of 5-20 wt.% of the total weight amount of the surfactant system.

7. A phosphate-free machine dishwash detergent composition according to any one of the preceeding claims, characterized in that the composition comprises 1.5-15 wt.% of a surfactant system containing

i) 0.05 - 2 wt.% of a C₁₀-C₁₈ alkyl dimethylamine oxide,

ii) 1.2 - 6 wt.% of an alkylpolyethylene glycol ether nonionic surfactant of the formula R¹-(EO)_xOH, wherein R¹ is a linear or branched alkyl group containing between 10 to about 18 carbon atoms and x is an integer between 20 and 180, preferably between 25 and 120,

iii) 0.1 - 12 wt.% of an alkylpolyethylene glycol ether nonionic surfactant of the formula R²-(EO)_xOH, wherein R² is a linear or branched alkyl group containing between 10 to about 18 carbon atoms and preferably between 11-15 carbon atoms, and x is between 5 and 12, preferably between 6 and 10,

and optionally, a further nonionic surfactant different from any of the nonionics of formula i), ii) or iii).

8. A phosphate-free machine dishwash detergent composition according to any one of the preceeding claims, characterized in that the composition comprises 2-10 wt.% of a nonionic surfactant system which contains

i) 0.1 - 1 wt.% of a C₁₀-C₁₈ alkyl dimethylamine oxide,

ii) 2 - 5 wt.% of an alkylpolyethylene glycol ether nonionic surfactant of the formula R¹-(EO)_xOH, wherein R¹ is a linear or branched alkyl group containing between 10 to about 18 carbon atoms and x is an integer between 20 and 180, preferably between 25 and 120,

iii) 0.5 - 5 wt.% of an alkylpolyethylene glycol ether nonionic surfactant of the formula R²-(EO)_xOH, wherein R² is a linear or branched alkyl group containing between 10 to about 18 carbon atoms and preferably between 11-15 carbon atoms, and x is between 5 and 12, preferably between 6 and 10, and optionally, a further nonionic surfactant different from any of the nonionics of formula i), ii), or iii) .

9. A phosphate-free machine dishwash detergent composition according to any one of claims 1-8, characterized in that the the composition comprises 30 wt% of at least one of MGDA, GLDA and IDS.

10. A phosphate-free machine dishwash detergent composition according to claim 3, wherein at least part of the composition is in the form of the liquid or gel, and composition comprises 15 - 70 wt% of a non-phosphate containing builder system comprising GLDA.

11. A phosphate-free machine dishwash detergent composition according to claim 8, wherein the composition further comprises enzymes.

Ansprüche

1. Zusammensetzung eines Phosphat-freien Maschinengeschirrspülmittels, umfassend

a) 15-70 Gew.-% eines kein Phosphat enthaltenden Builder-Systems, umfassend mindestens eines von Methylglycindiessigsäure (MGDA), Glutamindiessigsäure (GLDA) und Iminodisuccinsäure (IDS) und vorzugsweise 20-60 Gew.-% eines solchen Builder-Systems und bevorzugter 25-60 Gew.-% eines solchen Builder-Systems;

b) 0,1-15 Gew.-% eines nicht-ionischen Tensid-Systems, umfassend

i) ein C₁₀-C₁₈-Alkyldimethylaminoxid,

ii) ein nicht-ionisches Tensid in Form eines Alkylpolyethylenglycolethers der Formel R¹ - (EO)_x OH, worin R¹ eine lineare oder verzweigte Alkylgruppe ist, die zwischen 10 und 18 Kohlenstoffatome enthält, und x eine ganze Zahl zwischen 20 und 180, vorzugsweise zwischen 25 und 120, ist,

iii) optional ein nicht-ionisches Tensid in Form eines Alkylpolyethylenglycolethers der Formel R² - (EO)_x OH, worin R² eine lineare oder verzweigte Alkylgruppe ist, die zwischen 10 und 18 Kohlenstoffatome und vorzugsweise zwischen 11-15 Kohlenstoffatome enthält, und x zwischen 5 und 12, vorzugsweise zwischen 6 und 10, liegt,

iv) optional ein weiteres nicht-ionisches Tensid, das von i), ii) oder iii) verschieden ist;

wobei die Gewichtsmenge des C₁₀-C₁₈-Alkyldimethylaminoxids in dem Bereich von 2,5-30 Gew.-% der gesamten Gewichtsmenge des vorliegenden nicht-ionischen Tensidsystems liegt;

c) mindestens ein Bleichmittel oder Enzyme.

2. Zusammensetzung eines Phosphat-freien Maschinengeschirrspülmittels nach Anspruch 1, wobei die Zusammensetzung ein Bleichmittel und einen Mangankomplex-Bleichkatalysator umfasst.

3. Zusammensetzung eines Phosphat-freien Maschinengeschirrspülmittels nach irgendeinem der Ansprüche 1 oder 2, wobei mindestens 30 Gew.-% des kein Phosphat enthaltenden Builder-Systems (Gew.-%, bezogen auf das Gesamtgewicht des Builder-Systems) eine Amino(poly)carboxylverbindung darstellt, ausgewählt aus MGDA, GLDA und/oder IDS.

4. Zusammensetzung eines Phosphat-freien Maschinengeschirrspülmittels nach irgendeinem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Zusammensetzung 0,05-2 Gew.-% der Gruppe des nicht-ionischen Tensids in Form von C₁₀-C₁₈-Alkyldimethylaminoxid umfasst.

5. Zusammensetzung eines Phosphat-freien Maschinengeschirrspülmittels nach irgendeinem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das C₁₀-C₁₈-Alkyldimethylaminoxid aus der Gruppe des C₁₄-C₁₈-Alkyldimethylaminoxids ausgewählt ist.

6. Zusammensetzung eines Phosphat-freien Maschinengeschirrspülmittels nach irgendeinem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Menge der vorliegenden C₁₀-C₁₈-Alkyldimethylaminoxide in dem Bereich von 5-20 Gew.-% der gesamten Gewichtsmenge des Tensid-Systems liegt.

7. Zusammensetzung eines Phosphat-freien Maschinengeschirrspülmittels nach irgendeinem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Zusammensetzung 1,5-15 Gew.-% eines Tensid-Systems umfasst, enthaltend

i) 0,05-2 Gew.-% eines C₁₀-C₁₈-Alkyldimethylaminoxids,

ii) 1,2-6 Gew.-% eines nicht-ionischen Tensids in Form eines Alkylpolyethylenglycolethers der Formel R¹ - (EO)_x OH, worin R¹ eine lineare oder verzweige Alkylgruppe ist, die zwischen 10 und etwa 18 Kohlenstoffatome enthält, und x eine ganze Zahl zwischen 20 und 180, vorzugsweise zwischen 25 und 120, ist,

iii) 0,1-12 Gew.-% eines nicht-ionischen Tensids in Form eines Alkylpolyethylenglycolethers der Formel R²-(EO)_xOH, worin R² eine lineare oder verzweigte Alkylgruppe ist, die zwischen 10 und etwa 18 Kohlenstoffatome und vorzugsweise zwischen 11-15 Kohlenstoffatome enthält, und x zwischen 5 und 12, vorzugsweise zwischen 6 und 10, liegt, und optional ein weiteres nicht-ionisches Tensid, das von jeder der nicht-ionischen Verbindungen der Formel i), ii) oder iii) verschieden ist.

8. Zusammensetzung eines Phosphat-freien Maschinengeschirrspülmittels nach irgendeinem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Zusammensetzung 2-10 Gew.-% eines nicht-ionischen Tensid-Systems umfasst, das enthält

i) 0,1-1 Gew.-% eines C₁₀-C₁₈-Alkyldimethylaminoxids,

ii) 2-5 Gew.-% eines nicht-ionischen Tensids in Form eines Alkylpolyethylenglycolethers der Formel R¹ - (EO)_x OH, worin R¹ eine lineare oder verzweigte Alkylgruppe ist, die zwischen 10 und etwa 18 Kohlenstoffatome enthält, und x eine ganze Zahl zwischen 20 und 180, vorzugsweise zwischen 25 und 120, ist,

iii) 0,5-5 Gew.-% eines nicht-ionischen Tensids in Form eines Alkylpolyethylenglycolethers der Formel R² - (EO)_x OH, worin R² eine lineare oder verzweigte Alkylgruppe ist, die zwischen 10 und etwa 18 Kohlenstoffatome und vorzugsweise zwischen 11-15 Kohlenstoffatome enthält, und x zwischen 5 und 12, vorzugsweise zwischen 6 und 10, liegt und optional ein weiteres nicht-ionisches Tensid, das von jeder der nicht-ionischen Verbindungen der Formel i), ii) oder iii) verschieden ist.

9. Zusammensetzung eines Phosphat-freien Maschinengeschirrspülmittels nach irgendeinem der Ansprüche 1-8, dadurch gekennzeichnet, dass die Zusammensetzung 30 Gew.-% mindestens eines von MGDA, GLDA und IDS umfasst.

10. Zusammensetzung eines Phosphat-freien Maschinengeschirrspülmittels nach Anspruch 3, wobei mindestens ein Teil der Zusammensetzung in Form einer Flüssigkeit oder eines Gels vorliegt und die Zusammensetzung 15-70 Gew.-% eines kein Phosphat enthaltenden Builder-Systems, das GLDA einbezieht, umfasst.

11. Zusammensetzung eines Phosphat-freien Maschinengeschirrspülmittels nach Anspruch 8, wobei die Zusammensetzung ferner Enzyme umfasst.

Revendications

1. Composition de détergent pour lave-vaisselle exempte de phosphate comprenant

a) 15-70 % en masse d'un système d'adjuvant ne contenant pas de phosphate comprenant au moins un d'acide méthylglycine diacétique (MGDA), acide glutamique diacétique (GLDA) et acide imino disuccinique (IDS), et de préférence 20-60 % en masse d'un tel système d'adjuvant, et encore mieux 25-60 % en masse d'un tel système d'adjuvant;

b) 0,1-15 % en masse d'un système de tensioactif non-ionique comprenant

i) un oxyde d'alkyle en C₁₀-C₁₈ diméthylamine,

ii) un tensioactif non-ionique d'alkylpolyéthylène glycol éther de la formule R¹-(EO)_xOH, où R¹ est un groupe alkyle linéaire ou ramifié contenant de 10 à 18 atomes de carbone et x est un nombre entier de 20 à 180, de préférence de 25 à 120,

iii) éventuellement, un tensioactif non-ionique d'alkylpolyéthylène glycol éther de la formule R²-(EO)_xOH, où R² est un groupe alkyle linéaire ou ramifié contenant de 10 à 18 atomes de carbone et de préférence 11-15, et x est de 5 à 12, de préférence de 6 à 10,

iv) éventuellement, un autre tensioactif non-ionique différent de i), ii), ou iii) ;

dans laquelle la quantité de masse de l'oxyde d'alkyle en C₁₀-C₁₈ diméthylamine se trouve dans l'intervalle de 2,5-30 % en masse de la quantité de masse totale du système de tensioactif non-ionique présent ;

c) au moins un d'un agent blanchissant ou d'enzymes.

2. Composition de détergent pour lave-vaisselle exempte de phosphate selon la revendication 1, dans laquelle la composition comprend un agent blanchissant et un catalyseur de blanchiment de complexe de manganèse.

3. Composition de détergent pour lave-vaisselle exempte de phosphate selon l'une quelconque des revendications 1 ou 2, dans laquelle au moins 30 % en masse du système d'adjuvant de non-phosphate (% en masse rapporté à la masse totale du système d'adjuvant) est un composé amino (poly)carboxylique choisi parmi MGDA, GLDA et/ou IDS.

4. Composition de détergent pour lave-vaisselle exempte de phosphate selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition comprend 0,05-2 % en masse du groupe de tensioactif non-ionique d'oxyde d'alkyle en C₁₀-C₁₈ diméthylamine.

5. Composition de détergent pour lave-vaisselle exempte de phosphate selon l'une quelconque des revendications précédentes, caractérisée en ce que l'oxyde d'alkyle en C₁₀-C₁₈ diméthylamine est choisi dans le groupe d'oxyde d'alkyle en C₁₄-C₁₈ diméthylamine.

6. Composition de détergent pour lave-vaisselle exempte de phosphate selon l'une quelconque des revendications précédentes, caractérisée en ce que la quantité d'oxydes d'alkyle en C₁₀-C₁₈ diméthylamine présents se trouve dans l'intervalle de 5-20 % en masse de la quantité de masse totale du système de tensioactif.

7. Composition de détergent pour lave-vaisselle exempte de phosphate selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition comprend 1,5-15 % en masse d'un système de tensioactif contenant

i) 0,05-2 % en masse d'un oxyde d'alkyle en C₁₀-C₁₈ diméthylamine,

ii) 1,2-6 % en masse d'un alkylpolyéthylène glycol éther tensioactif non-ionique de la formule R¹-(EO)_xOH, où R¹ est un groupe alkyle linéaire ou ramifié contenant de 10 à environ 18 atomes de carbone et x est un nombre entier de 20 à 180, de préférence de 25 à 120,

iii) 0,1-12 % en masse d'un tensioactif non-ionique d'alkylpolyéthylène glycol éther de la formule R²-(EO)_xOH, où R² est un groupe alkyle linéaire ou ramifié contenant de 10 à environ 18 atomes de carbone et de préférence 11-15 atomes de carbone, et x est de 5 à 12, de préférence de 6 à 10,

et éventuellement, un autre tensioactif non-ionique différent des non-ioniques de formule i), ii) ou iii).

8. Composition de détergent pour lave-vaisselle exempte de phosphate selon l'une quelconque des revendications précédentes, caractérisée en ce que la composition comprend 2-10 % en masse d'un système de tensioactif non-ionique qui contient

i) 0,1-1 % en masse d'un oxyde d'alkyle en C₁₀-C₁₈ diméthylamine,

ii) 2-5% en masse d'un tensioactif non-ionique d'alkylpolyéthylène glycol éther de la formule R¹-(EO)_xOH, où R¹ est un groupe alkyle linéaire ou ramifié contenant de 10 à environ 18 atomes de carbone et x est un nombre entier de 20 à 180, de préférence de 25 à 120,

iii) 0,5-5 % en masse d'un tensioactif non-ionique d'alkylpolyéthylène glycol éther de la formule R²-(EO)_xOH, où R² est un groupe alkyle linéaire ou ramifié contenant de 10 à environ 18 atomes de carbone et de préférence 11-15 atomes de carbone, et x est de 5 à 12, de préférence de 6 à 10,

et éventuellement, un autre tensioactif non-ionique différent des non-ioniques de formule i), ii), ou iii).

9. Composition de détergent pour lave-vaisselle exempte de phosphate selon l'une quelconque des revendications 1-8, caractérisée en ce que la composition comprend 30 % en masse d'au moins un de MGDA, GLDA et IDS.

10. Composition de détergent pour lave-vaisselle exempte de phosphate selon la revendication 3, dans laquelle au moins une partie de la composition est dans la forme du liquide ou gel, et la composition comprend 15-70 % en masse d'un système d'adjuvant ne contenant pas de phosphate comprenant GLDA.

11. Composition de détergent pour lave-vaisselle exempte de phosphate selon la revendication 8, dans laquelle la composition comprend de plus des enzymes.