[0001] The invention relates to a composition for wet retanning and fatliquoring of pelts,
skins, hides, leather intermediate products or non-finished leather and to its production
and use.
[0002] For wet retanning and fatliquoring the leather industry is using different compounds,
especially polymeric compounds have been proposed for obtaining soft and firm leather
types.
[0003] US 5,279,613 discloses copolymers which are obtainable by free radical copolymerization of (a)
C
8-C
40-monoolefins with (b) ethylenically unsaturated C
4-C
8-dicarboxylic anhydrides by mass polymerization at from 80°C to 300°C to give copolymers
having molecular weights of from 500 to 20,000 g/mol, subsequent solvolysis of the
anhydride groups of the copolymers and partial or complete neutralization of the carboxyl
groups formed during the solvolysis, in an aqueous medium by means of a base, and
which are present in the form of aqueous dispersions or solutions, which are used
as agents for rendering leathers and skins water-repellent.
[0004] US 5,575,939 discloses a process for the fat liquoring/softening of leathers and furs by treatment
with an aqueous dispersion of a copolymer obtainable by polymerization of a) maleic
anhydride, b) C
12-C
30 alpha-olefins, esters of (meth)acrylic acid and/or maleic acid with C
12-C
30 alcohols and c) optionally, further hydrophilic, ethylenically unsaturated monomers
which are copolymerizable with a) and b), reaction of the anhydride groups with monovalent
alcohols comprising at least one ether functionality, and partial neutralization or
hydrolysis of the residual acid or anhydride groups and manufacture of a flowable
dispersion having an active substance content of at least 40%-wt.
[0005] Nevertheless there is always a need for compounds with even better properties.
[0006] It has now surprisingly been found that with the below defined composition, there
can be achieved in wet retanning and fatliquoring of pelts, skins, hides, leather
intermediate products or non-finished leather an outstanding and highly satisfactory
retanning and fatliquoring of the substrates.
[0007] Therefore an object of the instant invention is a composition consisting of the components
(A), (B) and (C) wherein:
- (A) is a reaction product of an ethylenically unsaturated C4-C8-dicarboxylic anhydride with C3-C40-alpha-olefins, used in acid form or preferably followed by partial or total neutralisation
with a base in aqueous dispersion with or without solvents, optionally part of the anhydride groups are reacted with alcohols, polyalcohols,
glycols or organic amines,
- (B) is a reaction product of ethylenically unsaturated C4-C8-dicarboxylic anhydrides with C10-C40-fatty acids or C4-C30 polycarboxylic acids or C10-C40 fatty alcohols or oxo-alcohols or glycols or polyglycols or C3-C20 organic amines, all being saturated or unsaturated, linear or branched and the fatty
acids being ethoxylated and/or propoxylated or having been reacted with polyglycols
or glycols, and the polycarboxylic acids being ethoxylated and/or propoxylated or
having been reacted with polyglycols or glycols at least with one carboxylic group,
whereas the fatty alcohols or oxo-alcohols and the fatty amines can optionally be
ethoxylated and/or propoxylated, and
- (C) is a reaction product of (B) with bisulphite or metabisulphite or sulphite or
sulphuric acid or oleum preferably neutralised with a base where the base is an alkali
or earth alkali hydroxide, ammonia or an organic amine in aqueous dispersion with
or without solvents.
[0008] In the component (B) the glycols or polyglycols can be reacted with other carboxylic
acids or C
4-C
30 polycarboxylic acids or derivates of carboxylic or polycarboxylic acids.
[0009] This composition provides excellent softening and retanning properties which can
make further treatment with retanning and lubricating agents unnecessary. It confers
outstanding chemical and physical properties to the leathers: excellent fogging values,
good light and heat stability, no spue problems, ecological advantage: low COD in
the bath, no phenol or formaldehyde in the bath as well as in the leather (usually
present in bath and leather after treatments with common retanning agents), properties
which otherwise are very difficult to reach with the standard fatliquoring and retanning
agents already available on the market.
[0010] Preferred are compositions wherein
in the component (A) the dicarboxylic anhydride is maleic anhydride and the alpha-olefins
have a chain length of 12 to 30 C-atoms and the base is ammonia, an amine or an alkali
or earth alkali hydroxide in aqueous dispersion with or without solvents,
in the component (B) the dicarboxylic anhydride is maleic anhydride, and the fatty
acids or fatty alcohols or oxo-alcohols have a chain length of 12 to 30 C-atoms and
are ethoxylated/propoxylated with 2- 25 mol of EO/PO (ethylene oxide/propylene oxide)
or the fatty acids are reacted with polyglycols 100 - 1200,
the component (C) is a reaction product of (B) with sodium bisulphite carried out
in aqueous dispersion.
[0011] Especially good properties show compositions wherein
in the component (A) the alpha-olefins have a chain length of 18 to 24 C-atoms and
the base is NaOH,
in the component (B) the fatty acids or fatty alcohols or oxo-alcohols have a chain
length of 12 to 20 C-atoms and have one or more double bonds, and the fatty acids
and fatty alcohols or oxo-alcohols have been ethoxylated and optionally the fatty
acids have been reacted prior to the reaction with maleic anhydride with polyethylene
glycols or glycols.
[0012] Examples of said fatty acids used for (B) are lauroleic acid, miristoleic acid, palmitoleic
acid, oleic acid, linoleic acid, or alpha-linolenic acid. Preferred are oleic acid
and linoleic acid or mixtures thereof, and especially preferred is oleic acid.
[0013] Preferred examples of said alcohols used for (B) are oleyl alcohol, linoleyl alcohol,
cetyloleylalcohols or mixtures thereof as well as branched alcohols from oxo-synthesis
like C
9, C
10, C
11, C
12, C
13 - C
14, C
15 oxo-alcohols or mixtures thereof.
[0014] Especially preferred compositions are those wherein
in the component (A) the alpha-olefins have a chain length of 20 to 22 C-atoms,
in the component (B) the fatty acid is oleic acid and wherein the polyethylene glycol
is a polyethylene glycol of the formula HO(CH
2CH
2O)
nH with an average number of n from 2 to 25 (like for example "polyglycol 100 - 1200").
[0015] The alpha-olefins used are commercial products. A chain length of 20 to 22 C-atoms
does not exclude smaller amounts (up to 10 mol-%) of C
18 or shorter and C
24 or longer.
[0016] The oleic acid used is a commercial product from natural sources , that means mixture
of fatty acids C
12-C
18 whereas the percentage of oleic acid is > 60%.
[0017] The instant compositions in general have a molar ratio of (A):[(B) + (C)] of from
5:100 to 100:5 and a molar ratio of (B):(C) of from 5:100 to 100:5.
[0018] Preferred are compositions wherein the molar ratio of (A):[(B) + (C)] is from 50:100
to 100:50, more preferably from 70:100 to 100:70 and the molar ratio from (B):(C)
is from 20:100 to 100:20, more preferably from 60:100 to 100:60.
[0019] The instant compositions may further comprise amides and esters of (A) as described
in
US 5,279,613. Details of these amidation and esterification reactions are found in this prior
art.
[0020] The instant compositions may further comprise at least one formulation additive (S)
e.g. for adjusting the physical aspect of the composition and/or its use properties
and may be selected from water or an organic solvent or a solubiliser or mixtures
thereof, said additives being miscible with or soluble in (A) and (B) and (C) or in
which (A) and (B) and (C) are soluble. Furthermore at least one of the following additives
or mixtures thereof may be contained: defoamers, natural or mineral oils, surfactants,
lecithines, biocides.
[0021] (S) may in particular comprise one or more solvents and/or solubilisers and/or a
defoamer and/or one or more surfactants and/or mineral or natural oil and/or a biocide.
Preferably (S) is selected from the group comprising (S1) water, (S2) an organic solvent
or mixture of organic solvents and/or a solubiliser or mixture of solubilisers, miscible
with or soluble in (A) and (B) and (C) or in which (A) and (B) and (C) are soluble,
(S3) a defoamer and/or (S4) a surfactant and/ or (S5) a mineral or natural oil and/or
(S6) synthetic or natural lecithine and/ or (S7) a biocide.
[0022] Preferably (S2) is an organic solvent miscible with water, which is aliphatic and
contains at least one oxygen and no other heteroatoms, or a mixture of two or more
of such solvents. More preferably (S2) is selected from the group consisting of aliphatic
mono- or oligofunctional alcohols and mono- or di-(C
1-C
4-alkyl)-ethers thereof. (S2) may include water-miscible, saturated aliphatic solvents
of ether and/or alcohol character. As (S2) there may in particular be employed a C
3-C
4-alkanol, a diol which is a C
2-C
4-alkylene glycol or a higher diol e.g. with 6 carbon atoms mainly 2-methyl-2,4-pentanediol
(hexylene glycol), dipropylene glycol or a di-. tri- or tetraethylene glycol, and
mono- or di-(C
1-C
4-alkyl)-ethers thereof, or glycerol. Particularly preferred solvents or solubilisers
(S2) include e.g.: isopropanol, mono- or dipropylene glycol, mono-, di-, tri- or tetraethylene
glycol, hexylene glycol, mono- or dipropylene glycol monomethylether, ethylene glycol
monobutylether and methyl, ethyl, isopropyl or butyl mono- or diethers of di-, tri-
or tetraethylene glycol.
[0023] As solvents/solubilisers in (S) there may be employed water (S1) alone, solvent or
solubiliser (S2) alone or a mixture of water (S1) and solvent or solubiliser (S2).
[0024] As defoamers (S3) there may be employed known products in the commercially available
forms, like, for example, silicones, silica, paraffins, paraffin oil, mineral oil
or trialkylphosphates (e.g. triisopropyl-phosphate or tributylphosphate), ethers,
alkoxylated fatty esters, alkoxylated fatty acids, in an efficient concentration,
e.g. below 0.2 % by weight, preferably below 0.1% by weight, referred to the dry content
of (A)+(B)+(C). Mostly a defoamer (S3) is not necessary and is not added.
[0025] As surfactants (S4) there may be employed any conventional non ionic or anionic surfactants
in particular with emulsifier character.
[0026] As non ionic surfactants are preferably employed alkoxylated, mainly ethoxylated,
alcohols. As alkoxylated alcohols can also be employed some alkoxylated, preferably
ethoxylated oxo-alcohols.
[0027] As anionic surfactant preferably emulsifiers contain a sulpho group, optionally a
phosphorus group. Preferably as anionic surfctant (S4) are employed arilaliphatic
or more preferably aliphatic sulphates, which may contain a heteroatomic bridge in
the aliphatic chain (e.g. an ester, amine, amide or preferably ether bridge) and which
contain a lipophilic hydrocarbon radical e.g. with 7 to 24 carbon atoms, more preferably
sulphuric acid monoesters of fatty alcohols or of ethoxylated (e.g. mono- to oligo-ethoxylated)
fatty alcohols or fatty amine with e.g. 12 to 24 carbon atoms in the fatty hydrocarbon
radical. Among these the sulphuric acid esters of ethoxylated fatty alcohols are preferred.
Optionally as anionic surfactant are employed arilaliphatic or more preferably aliphatic
mono- or di-phosphoric acid esters or mixture thereof. Among these the phosphoric
acid esters of ethoxylated fatty alcohols are preferred.
[0028] The anionic surfactants (S4) are preferably in the form of alkali metal salts, more
preferably sodium or potassium salts.
[0029] As mineral or natural oils (S5) may be employed hydrocarbons fluid got by distillation
of the oil, paraffinic hydrocarbons and / or natural or synthetic waxes or vegetable
or animal tryglycerides.
[0030] If desired to modify the applicative properties may be employed synthetic or natural
lecithine (S6). Mostly the lecithine is not necessary and is not added.
[0031] As biocide (S7) there may be employed known products in the commercially available
forms, e.g biocide based on 1,2-benzoisotiazolin-3-one and 1,2-dibromo-2,4-dicianobutano,
biocide based on chloro or chloro free isotiazolinoni, based on bronopol, based on
2-(tiocianometiltio)-benzotiazolo or based on p-cloro-m- cresol. These products can
be employed alone or in mixture.
[0032] The polymers (A) are basically known products and are for example described in
US 5,279,613,
US 5,575,939 or
DE 3 730 885. Details of their preparation are also disclosed in these documents.
[0033] The instant compound (B) is not a polymerization product where a radical polymerization
takes place and therefore still contains double bonds, in contrast to the product
of
US 5,575,939 where a radical polymerization takes place.
[0034] Component B can be obtained by heating the mentioned starting compounds at a temperature
in the range 80 - 160 °C, with water distillation if required, optionally under vacuum
for 2 - 6 hours and in the presence of an organic solvent, if necessary.
[0035] The ethoxylated products or ethoxylated and propoxylated products (fatty acids, fatty
alcohols, oxo-alcohols) are known or may be produced in a manner conventional per
se by addition reaction of ethylene oxide or of ethylene oxide and propylene oxide
to the mixtures of fatty acids, fatty alcohols, oxo-alcohols, or organic amines.
[0036] As ethoxylation there is meant herein the addition reaction of ethylene oxide (also
known as oxyethylation). As propoxylation there is meant herein the addition reaction
of propylene oxide (also known as oxypropylation).
[0037] The addition reaction may be carried out under reaction conditions known per se,
preferably in the presence of an alkali metal hydroxide, e.g. sodium hydroxide or
potassium hydroxide, with heating, e.g. at a temperature in the range of 90 to 240°C,
preferably 130 to 220°C in a closed vessel, in the presence of an inert gas, e.g.
nitrogen. If propylene oxide is also reacted, it is preferably reacted first, followed
by the reaction of ethylene oxide. Propylene oxide, if used, is employed in a minor
proportion, preferably in this case there being added 1 to 2 moles of propylene oxide
per mole of fatty acids or fatty alcohols or oxo-alcohols or organic amines mixture;
more preferably no propylene oxide is added, but the mixture of fatty acids or fatty
alcohols or oxo-alcohols or organic amines is reacted only with ethylene oxide. The
molar proportion of ethylene oxide referred to fatty acids or fatty alcohols or oxo-alcohols
or organic amines or mixtures thereof is in the range of 2 to 25, preferably 6 to
14.
[0038] The reaction of fatty acids with polyglycols can be carried out at a temperature
in the range of 80-160°C for 2 - 6 hours optionally under vacuum (like for example
50-70 mm Hg), preferably with an acid catalyst like methansulfonic acid, as example.
[0039] Parts of component (B) are further reacted to synthesize (C) with sodium bisulphite
at a temperature in the range of 60-120 °C for 2-10 hours in the presence of water,
earth alkali hydroxides and, if necessary, organic solvents (like for example 2-propanol).
The preferable pH range during the reaction is 5-8.
[0040] The compositions of the invention may be produced in a manner conventional per se,
e.g. by mixing the components (A), (B) and (C) and any formulation additive (S).
[0041] The admixing of (A) with (B) and (C) and any (S) may be carried out e.g. at a temperature
in the range of 15 to 70°C.
[0042] More preferably the corresponding mixture of (B) and (C) is prepared in a reactor
with the required addition of sulphite or bisulphite or sulphuric acid or oleum agent
to (B) and follows the neutralization with a base in the presence of water and, if
necessary, organic solvents, and then (A) is added and (S) is added, if desired, at
a temperature in the range of 15 to 70°C.
[0043] Of course, it is also possible to add the mixture of (B) and (C) to the component
(A) that can already be added with (S), if desired, mixing all the components at a
temperature in the range of 15 to 70°C.
[0044] It is also possible to add the mixture of (B) and (C) to the component (A) and then
(S) is added, if desired, mixing all the components at a temperature in the range
of 15 to 70°C.
[0045] The so produced compositions are ready for use. They are of satisfactory stability
to storage and transportation. They are readily dilutable with water resulting in
an aqueous dispersion and may e.g. be directly dosed into the treatment bath.
[0046] The aqueous dispersions thus obtainable are stable and have a long shelf life. They
are very suitable for treating leathers and skins because they have a particularly
pronounced action in fatliquoring and retanning. In many cases no additional fatliquoring
agents based on natural or synthetic fatliquoring oils are required. The dispersions
impart to the product good body and high tensile strength and tear strength, so that
additional treatment with commercial retanning agents, for example with vegetable
tanning agents or synthetic organic tanning agents (syntans) based on phenolsulfonic
acid/phenol/formaldehyde condensates, is no longer necessary in most cases.
[0047] The dispersions described above are suitable for the treatment of all conventional
tanned hides, in particular hides tanned with mineral tanning agents, such as chromium(III)
salts.
[0048] The invention further provides a process for wet retanning and fatliquoring of tanned
pelts, skins, hides, leather intermediate products or non-finished leather (crusted
leather) or pelts, characterised in that a composition as defined above is employed
as a retanning and fatliquoring agent.
[0049] In particular the invention provides a process for the production of leather, pelts
or furskins, comprising in their production at least a wet degreasing treatment, a
tannage, a retanning, a fatliquoring and a dyeing or finishing treatment, wherein
retanning and fatliquoring can be carried out in one step with the instant composition
or completed, if desired, with other commercial fatliquoring and retanning products.
[0050] As a substrate according to the invention there may be employed any hides, skins
or pelts as conventionally processed in the beamhouse, tanned conventionally to get
a wet blue or wet white leathers. There may e.g. be mentioned pelts, hides or skins
from cow, sheep, goat, swine, cattle and other animals (e.g. horse, colt, reptiles
- e.g. snake, lizards, water reptiles -, doe, deer, ostrich, poultry, dromedary, camel
and camel-like animals - e.g. lama or alpaca -), and woolled skins (mainly from sheep
or goat) and furskins.
[0051] Retanning and fatliquoring according to the invention may also be applied to leather
intermediate products or non-finished leather (crusted leather). Thus if the substrate
has already been tanned or retanned, the instant composition may be used before dyeing,
mostly in order to improve dyeability e.g. uniform dispersion and distribution of
the dye, or after dyeing to confer a fuller and deeper dyeing, or before finishing
in order to prepare the substrate for a particular uniform link of the finishing.
[0052] To the retanning and fatliquoring bath there may e.g. be added one or more anionic
surfactants (G) and/or a water miscible solvent (H).
[0053] As surfactants (G) of anionic character there may be employed any conventional surfactants,
preferably those containing a sulpho group, e.g. aliphatic or arylaliphatic sulphates
(G
1) or sulphonates (G
2), which may contain a heteroatomic bridge in the aliphatic chain (e.g. an ester,
ether or preferably amide, bridge, an ether bridge being with particular preference
part of a glycol ether chain) and which contain a lipophilic hydrocarbon radical e.g.
with 7 to 24 carbon atoms. They are preferably in the form of alkali metal salts,
more preferably sodium or potassium salts.
[0054] Suitable sulphates (G
1) are e.g.:
- (G1')
- sulphuric acid monoesters of fatty alcohols or of ethoxylated (e.g. mono-to oligo-ethoxylated)
fatty alcohols or fatty amine with e.g. 12 to 24 carbon atoms in the fatty hydrocarbon
radical,
- (G1")
- sulphuric acid esters of fatty acid monoglycerides with e.g. 12 to 24 carbon atoms
in the fatty acid radical,
- (G1"')
- products of sulphation of unsaturated fatty acids or unsaturated oils (fatty acid
triglycerides) with e.g. 18 to 22 carbon atoms in the unsaturated fatty acid radical
or of ricinoleic acid or castor oil.
[0055] Suitable sulphonates (G
2) are e.g.
- (G2')
- fatty alkyl sulphonates and isothionates, with e.g. 12 to 24 carbon atoms in the fatty
hydrocarbon radical, petroleum sulphonate (mainly secondary sulphonates with e.g.
10 to 15, usually 12 to 13, carbon atoms in the aliphatic chain),
- (G2")
- fatty acid taurides and N-methyltaurides with e.g. 12 to 24 carbon atoms in the fatty
acid radical,
- (G2'")
- products of sulphitation of unsaturated fatty acids or unsaturated oils (fatty acid
triglycerides) with e.g. 16 to 24 carbon atoms in the unsaturated fatty acid radical,
- (G2"")
- mono- and di-alkyl-benzene sulphonates with e.g. a total of 1 to 12 carbon atoms in
the alkyl substitution, e.g. with 4 to 12 carbon atoms in the alkyl chain, or short
chain alkyl-benzene sulphonates with 1 to 3 carbon atoms in the alkyl radical and
in the total alkyl substitution.
[0056] As mono- to oligo-ethoxylated in (G
1') there is meant the addition product of 1 to 10 moles of ethylene oxide to one mole
of fatty alcohol. As examples of (G
1) there may be mentioned in particular lauryl sulphate, stearyl sulphate, and the
sulphates of the addition product of 1 to 6 moles of ethylene oxide to one mole of
lauryl or stearyl alcohol. As examples of (G
2) there may be mentioned in particular toluene-, xylene- or cumene-sulphonic acids,
and fatty acid taurides or N-methyl taurides with on average 16 to 20 carbon atoms
in the fatty acid radical. They are preferably in the form of potassium salts or more
preferably sodium salts.
[0057] The solvents (H) are water-miscible, organic, preferably aliphatic solvents containing
at least two linked oxygen atoms per molecule in the form of alcoholic hydroxy groups
and/or ether bridges, and are in particular exempt of other heteroatoms than oxygen.
There may in particular be mentioned saturated aliphatic compounds of ether and/or
alcohol character, mainly mono-, di-, tri- and/or tetra-alkylene glycols and their
mono-or di-(C
1-4-alkyl) ethers, preferably with ≥ 4 carbon atoms in the molecule, more preferably
with ≥ 6 carbon atoms, e.g. butane-2,3- or -1,4-diol, dipropylene glycol, monomethyl
ether of mono- or dipropylene glycol, and methyl-, ethyl-, isopropyl- or butyl-ethers
of mono-, di-, or triethylene glycol, among which the monoalkylethers are preferred,
especially diethylene glycol mono-butyl ether.
[0058] According to one feature of the invention one or more anionic surfactants (G) and/or
a water miscible solvent (H) can be added to the instant composition.
[0059] Wet retanning and fatliquoring with the instant composition may be carried out analogously
to methods known per se, expediently in a treatment drum or in a rotated aqueous bath
e.g. in the range of 3 to 100 %, preferably 5 to 40 %, more preferably 5 to 15 % by
weight referred to the wet shaved weight of the substrate for tanned leathers (wet
blue leather or wet white leathers) and to the dry weight of the substrate for crusted
leathers.
[0060] The temperature T of the retanning and fatliquoring bath advantageously is in the
range of 20 to 60°C, preferably 30 to 60°C. The pH may be as desidered and advantageously
is in the range 3,0 - 6,5 .
[0061] Retanning and fatliquoring may be carried out in one or more stages, and in each
stage it may be carried out in one or more steps, preferably two, even if one is already
sufficient to get a good penetration and an homogeneous dispersion of the agents.
If it is carried out in two steps, one step may be regarded as the main step for the
retanning and fatliquoring, while the second step may be regarded as a follow-up step
for improving the effects and the substrate properties.
[0062] According to one feature of the invention, the instant composition may be used alone
or if desired in the presence of one or more further retanning or other fatliquoring
products expecially if leathers are manufactured to get particular articles, like
automotive upholstery leathers.
[0063] According to one feature of the invention at least a part of said composition may
be combined with other retanning or fatliquoring products. Preferably, however, any
or at least the major required proportion of other retanning or fatliquoring agents
are added separately to the bath, as desired and as suitable in the concerned treatment
stage and/or step.
[0064] For retanning and fatliquoring of
tanned substrates it is of advantage to use for the setting of bath and also for rinsing
from 100-400 % of water and of an organic acid like formic acid, acetic acid etc.,
e.g. of a concentration in the scope from 0.1 to 5 %, preferably 0.1 to 0.5 % by weight
and 0.2 - 3.0 % of a common wetting agent (a single component or a formulation) referred
to the wet shaved weight of the substrate.
[0065] As wetting agent can be employed one or more anionic surfactants and one or more
non ionic surfactants, preferably is employed one of more formulations of these surfactants
present on the market for this scope.
[0066] Then the substrate is drained, the bath is added with water from 50 to 300 %, the
pH is increased by addition of conventional bases or buffer salts such as sodium acetate,
sodium formiate from 1.0 to 4.0 % or sodium bicarbonate from 0.5 to 3.0 % or other
products having neutralising/buffering properties.
[0067] The bath is drained, again well washed with water from 50 to 400 % and drained again.
[0068] The retanning and fatliquoring treatment of the invention may be carried out for
a duration as conventional per se for retanning and fatliquoring e.g. in the range
of 1 to 4 hours, preferably 40 - 70 minutes for every treatment stage (in one or two
steps).
[0069] For retanning and fatliquoring of
crusted substrates it is of advantage to use for the setting of bath and also for rinsing
from 200-800 % of water and of an organic acid like formic acid or acetic acid, e.g.
of a concentration in the scope from 0.2 to 5 %, preferably 0.2 to 2.0 % by weight
and 0.2 - 4.0 % of a wetting agent (alone or in formulation as many are available
on the market) referred to the dry weight of the substrate.
[0070] As wetting agent can be employed one or more anionic surfactants and one or more
non ionic surfactants, preferably is employed one of more formulations of these surfactants
present on the market for this scope.
[0071] Then the substrate is drained, the bath is added with water from 100 to 600 % , the
pH is increased by addition of conventional bases or buffer salts such as sodium acetate,
sodium formiate from 2.0 to 8.0 % or sodium bicarbonate from 1.0 to 6.0 % or other
products having neutralising/buffering properties.
[0072] The substrate is drained, again well washed with water from 100 to 800 % and drained
again.
[0073] The retanning and fatliquoring treatment of the invention may be carried out for
a duration as conventional per se for retanning and fatliquoring e.g. in the range
of 1 to 4 hours, preferably 40 - 70 minutes for every treatment stage (in one or two
steps).
[0074] After completion of the retanning and fatliquoring treatment, which preferably is
followed by adjustments of pH or washing, the substrate may be directly further processed
in the foreseen sequence of treatments for the production of the leather or pelt as
desired. If desired, the retanning and fatliquoring substrates may even be washed,
eventually added with biocides, drained and dried, for being e.g. stored or shipped
in order to be further treated at a later stage. Preferably, however, the treatment
sequence is not interrupted after retanning and fatliquoring, but the substrate is
further treated in the same apparatus. The substrate retanned and fatliquored according
to the invention is readily and optimally suitable for each of the subsequent treatments.
[0075] By the process of the invention there may be achieved an outstanding degree of retanning
and fatliquoring of the substrate at once. In particular may be achieved a surprisingly
good retanning and fatliquoring, without impairing other characteristic properties
of the substrate, such as quality of the leather structure (especially the grain structure),
handle, dyeability, light fastness, heat fastness, fogging of the finished leathers
while a subsequent treatment with any chemicals finds in the substrate retanned and
fatliquored according to the invention a substrate of high suitability for even distribution
of the applied products, e.g., filling agents, other (re)tanning agents, dyestuffs,
pigments, leather softeners, so that dyed and/or finished leathers and pelts of optimum
quality are obtainable with a high yield of the corresponding applied products.
EXAMPLES
[0076] The following examples shall explain the instant invention in more detail. If not
indicated otherwise, parts and percentages are by weight and in the Application Examples
the percentages refer to the wet shaved weight of the substrate, if not otherwise
indicated. The starting materials employed in Examples and the additives employed
in the Application Examples further to the retanning and fatliquoring agent, are commercially
available products. The water used is a soft - middle hard water (max. 13-14 °F of
hardness).
[0077] I.U.C. standards mentioned in the Application Examples are international standards
in leather testing as recommended in IULTCS (International Union of Leather Technologists
and Chemists Societies)
PREPARATION EXAMPLES
EXAMPLE 1
[0078] 196 g of oleic acid are charged in a reactor and, under stirring, 139.0 g of polyglycol
200 are added and 1.3 g methan sulfonic acid are added. The mixture is heated up to
90-105 °C under vacuum (residual pressure of 50-70 mm Hg in reactor) and maintained
at that temperature for 3-4 hours distillating water (water to be destilled: 12,5
g).
[0079] 323,8 g. of reaction mass is cooled down to 80-90 °C and added with 34.1 g. of maleic
anhydride. A weak exothermic reaction takes place. Then the reaction mass is heated
up to 88 - 92 °C and kept at 88 - 92 °C for 30-40 minutes.
[0080] Then within 2-3 hours the temperature of the mass is increased to 100 - 110 °C under
vacuum (residual pressure in reactor is 50-60 mmHg ): condensation water is destilled.
[0081] The reaction mass is then heated up to 120 - 130 °C and kept at 120 - 130 °C for
2-3 hours, destilling water. Amount of water to be destilled: 6,3 g. of water.
[0082] Yield of reaction: 351,6 g
EXAMPLE 2
[0083] 351,6 g of product prepared as indicated in example 1 are charged in reactor and
heated to 80 - 90 °C and added with an aqueous solution of sodium metabisulphite and
NaOH, prepared by mixing 88 parts of water with 33 parts of metabisulphite and 27.5
parts of NaOH sol. 30%.
[0084] The mixture is heated up to 85-98 °C for 2-3 hours.
EXAMPLE 3
[0085] 745 g of α-olefine are charged in a dry reactor and heated up to 148-152 °C. At 140-145°C
36 g of ditert-butylperoxide are added. Then during one hour, 275 g of maleic anhydride,
melted at 80-90° C, are added under nitrogen flow and at a temperature of 150-165°C.
When the addition is finished the mixture is heated three hours at 155-165°C. At the
end of the reaction, the polymerization product is poured into an aqueous solution
pre-heated at 80°C of 3200g of water and 475 g of sodium hydroxide 30% sol. The mixture
is stirred one hour at 88-92°C and then cooled at 30-35°C.
EXAMPLE 4
[0086] 472 g prepared as indicated in example 2 are heated at 40-50 °C and mixed with 500
g of the product obtained in example 3.
APPLICATION EXAMPLES
APPLICATION EXAMPLE A
[0087] Retanning and fatliquoring of wet blue cow leathers, thickness: 1,5-1,6 mm (percentages
are based on the shaved weight).
[0088] Wet Blue leathers (half of a leather) are given into a drum and 300 % of water at
40°C are added, followed by 0.2 % of formic acid and the drum is rotated for 15 minutes.
The bath is drained. Then 150 % of water and 2 % of sodium formate and 1 % of sodium
bicarbonate arc added and drumming is continued for 60 minutes at 35-40 °C. The pH
is increased to 5.0. The bath is drained. 200 % of water at 35°C is added and the
goods are washed for 10 minutes, then the bath is drained. 100 % of water at 40 °C,
10 % of the instant retanning and lubricating composition are added and the drum is
rotated for 60 minutes at this temperature. 0.5 % of formic acid is added and the
drum is rotated for 10 minutes at 40 °C. Other 0.5 % of formic acid is added and the
drum is rotated for 20 minutes 40 °C: pH is 3.6.
[0089] The bath is drained. 300 % of water at 25°C is added and the goods are washed for
10 minutes, then the bath is drained and leathers are discharged, horsed up and dried
with one of the conventionally dry system (samm/sett out/vac dry/Hang dry/condition/stake/air
off), staked for assessing the properties of the leathers and the light, heat fastness
as well as the fogging.
[0090] The leather is retanned and fatliquored very regularly, is firm, tight, soft and
is optimally suitable for further processing in the tannery. Light and heat resistances
are good, fogging values are excellent.
APPLICATION EXAMPLE B
[0091] Retanning and fatliquoring of wet blue cow leathers, thickness 1.1 - 1.2 mm (percentages
are based on the shaved weight).
[0092] Wet Blue leathers (half of a leather) are given into a drum and 300 % of water at
40°C are added, followed by 0.2 % of formic acid and the drum is rotated for 20 minutes.
The bath is drained. Then 100 % of water, 2 % of a neutralising Syntan (like Tanicor
AS 6), 1.5 % of sodium bicarbonate and 3.0 % of the instant composition are added
and drumming is continued for 75 minutes at 35 - 40 °C. The bath is drained. 300 %
of water at 40°C is added and the goods are washed for 10 minutes, then the bath is
drained. 100 % of water at 40 °C, 3 % of the instant retanning and lubricating composition
are added and drumming is continued for 20 minutes, 3 % of a polyacrylate 30 % sol
(like Tergotan PR) is added and drumming is continued for 20 minutes, 4.0 % of a phenol/cresol
synthan (like Sandotan SG powder) and 4.0 % of TARA powder (vegetable tanning agent)
are added and drumming is continued for 30 minutes, 3 % of Dye (Melioderm Deep Brown
F) is added and drumming is continued for 60 minutes, 0.5 % of formic acid are added
and the drum is rotated for 15 minutes at this temperature, 1.0 % of formic acid is
added and the drum is rotated for 30 minutes at 35 -40 °C.
[0093] The bath is drained. 200 % of water at 60 °C is added and the goods are washed for
10 minutes, then the bath is drained. 150 % of water is added and 8.0 % of the instant
retanning and lubricating composition is added and the drum is rotated for 60 minutes
at 60 °C. 0.5% of formic acid is added and the drum is rotated.
[0094] Then the bath is drained and leathers are discharged, horsed up and dried with one
of the conventionally dry systems (samm/sett out/vac dry/Hang dry/condition/stake/air
off), staked, for assessing the properties of the leathers
[0095] The leather is retanned and fatliquored very regularly, is firm, tight, very soft
and is optimally suitable for further processing in the tannery.
APPLICATION EXAMPLE C
[0096] Retanning and fatliquoring of wet blue caw leathers, thickness 1.5 - 1.6 mm (percentages
are based on the shaved weight).
[0097] Wet Blue leather (half of a leather) are given into a drum and 200 % of water at
30°C are added, followed by 1.0 % of a wetting agent (like Tergolix W 01) and 0.5
% of acetic acid and the drum is rotated for 30 minutes. The bath is drained. Then
50 % of water at 35 °C, 5 % of Baychrom F (Chrom basic sulphate) are added and drumming
is continued for 90 minutes at 35 - 40 °C. The leather is left in the bath during
the night.
[0098] At the morning pH is 3.5. 100 % of water of 7°Bé at 50°C and 1 % of sodium formate
are added and the drum is rotated for 30 minutes. pH is 4.8. The bath is drained.
100 % of water of 7°Bé at 35 °C, 1 % of sodium formiate are added and rotated for
20 minutes, 1% of sodium bicarbonate is added and rotated for 40 minutes. pH is 5.6-5.7.
The leathers are washed with 300 % of water. The bath is drained. 100 % of water at
40 °C, 20 % of a phenol synthan 50% sol (like Syncotan MRL) are added and drumming
for 60 minutes. 1% of formic acid is added and drum is rotated for 20 minutes. The
bath is drained.
[0099] 50 % of water is added at 20 °C, 1% of Dye (Bruno Melioderm G) is added and drum
is rotated for 30 minutes. 100 % of water at 50 °C, 10 % of the instant retanning
and fatliquoring composition is added and the drum is rotated for 60 minutes. 1% of
formic acid is added and the drum is rotated for 20 minutes. The bath is drained.
[0100] 200 % of water at 15 °C is added and the drum is rotated for 10 minutes. The bath
is drained and the leathers are discharged and dried with one of the conventionally
dry system (samm/sett out/vac dry/Hang dry/condition/stake/air off), staked, for assessing
the properties of the leathers.
[0101] The leather is retanned and fatliquored very regularly, is firm, tight, soft and
are optimally suitable for further processing in the tannery.
Article: |
Heat & Light Fastness-Fatliquors |
Thickness: |
1.5mm |
Raw Material: |
Wet Blue |
Method: |
Direct |
Origin: |
LGR |
Colour: |
Natural |
Tannage: |
Chrome |
% Based on: |
Shaved Weight |
Date: |
|
Trial Number: |
1201 |
Process |
% |
Chemicals |
°C |
|
Min. |
pH |
Comments |
WASH |
300 |
Water |
40 |
|
|
|
|
|
0.2 |
Formic Acid |
|
|
15 |
|
|
DRAIN |
|
|
|
|
|
|
|
NEUTRALISE |
150 |
Water |
35 |
|
|
|
|
|
2.0 |
Sodium Formate |
|
|
|
|
|
|
1.0 |
Sodium Bicarbonate |
|
|
60 |
5,0 |
Cut: |
DRAIN |
|
|
|
|
|
|
|
WASH |
200 |
|
|
|
10 |
|
|
DRAIN |
|
|
|
|
|
|
|
RETAN |
100 |
Water |
40 |
|
|
|
|
|
10.0 |
Composition as described above |
|
|
60 |
|
|
+ |
0.5 |
Formic Acid |
|
|
10 |
|
|
+ |
0.5 |
Formic Acid |
|
|
20 |
3,6 |
|
DRAIN |
|
|
|
|
|
|
|
WASH |
300 |
Water |
25 |
|
10 |
|
|
DRAIN |
|
|
|
|
|
|
|
HORSE UP |
|
|
|
|
|
|
|
SAMM/SETT OUT/VAC DRY/HANG DRY/CONDITION/STAKE/AIR OFF |
Customer: |
Internal |
|
|
Article: |
Upholstery-Automotive |
Thickness: |
1.1 - 1.2 mm |
Raw: Material |
Wet Blue |
Method: |
Direct |
Origin: |
LGR |
Colour: |
Brown |
Tannage: |
Chrome |
% Based on: |
shaved weight |
Date: |
13.07.2006 |
Trial Number: |
1201 |
Process |
% |
Chemicals |
°C |
|
Min. |
pH |
Comments |
WASH |
300 |
Water |
40 |
|
|
|
|
|
0.2 |
Formic Acid |
|
|
20 |
|
|
DRAIN |
|
|
|
|
|
|
|
NEUTRALISE |
100 |
Water |
40 |
|
|
|
|
|
2.0 |
TANICOR AS6 |
|
|
|
|
|
+ |
1.5 |
Sodium Bicarbonate |
|
|
|
|
|
+ |
3.0 |
Composition D as described above |
|
|
75 |
|
|
DRAIN |
|
|
|
|
|
|
|
WASH |
300 |
Water |
40 |
|
10 |
|
|
DRAIN |
|
|
|
|
|
|
|
RETAN |
100 |
Water |
40 |
|
|
|
|
|
3.0 |
Composition as described above |
|
|
20 |
|
|
+ |
3.0 |
TERGOTAN PR |
|
|
20 |
|
|
+ |
4.0 |
SANDOTAN SG Powder |
|
|
|
|
|
+ |
4.0 |
Tara |
|
|
30 |
|
|
+ |
3.0 |
Sandoderm Deep Brown F |
|
|
60 |
|
|
+ |
0.5 |
Formic Acid |
|
|
15 |
|
|
+ |
1.0 |
Formic Acid |
|
|
30 |
|
|
DRAIN |
|
|
|
|
|
|
|
WASH |
200 |
Water |
60 |
|
10 |
|
|
DRAIN |
|
|
|
|
|
|
|
FAT |
150 |
Water |
60 |
|
|
|
|
|
8.0 |
Composition as described above |
|
|
60 |
|
|
+ |
0.5 |
Formic Acid |
|
|
30 |
|
|
DRAIN |
|
|
|
|
|
|
|
WASH |
300 |
Water |
20 |
|
10 |
|
|
DRAIN & UNLOAD |
|
|
|
|
|
|
|
SAMM/SET OUT/TOGGLE DRY/CONDITION/STAKE (7+7 twice through machine)/ASSESS/MILL 24
HRS/ ASSESS |
1. A composition comprising the components (A), (B) and (C) wherein
(A) is a reaction product of an ethylenically unsaturated C4-C8-dicarboxylic anhydride with C3-C40-alpha-olefins followed by partial or total neutralisation with a base, in aqueous
dispersion with or without solvents,
(B) is a reaction product of ethylenically unsaturated C4-C8-dicarboxylic anhydrides with C10-C40-fatty acids or C4-C30 polycarboxylic acids or C10-C40 fatty alcohols or oxo-alcohols or glycols or polyglycols or C3-C20 organic amines all being saturated or unsaturated, linear or branched and the fatty
acids being ethoxylated and/or propoxylated or having been reacted with polyglycols
or glycols, and the polycarboxylic acids being ethoxylated and/or propoxylated or
having been reacted with polyglycols or glycols at least with one carboxylic group,
whereas the fatty alcohols or oxo-alcohols and the fatty amines can optionally be
ethoxylated and/or propoxylated,
and
(C) is a reaction product of (B) with bisulphite or metabisulphite or sulphite or
sulphuric acid or oleum, followed by partial or total neutralization with a base where
the base is an alkali or earth alkali hydroxide, ammonia or an organic amine in aqueous
dispersion with or without solvents.
2. Composition according to claim 1 wherein
in the component (A) a part of the anhydride groups are reacted with alcohols, polyalcohols,
glycols or organic amines, or ammonia
in the component (B) the fatty alcohols or oxo-alcohols and the fatty amines have
been ethoxylated and/or propoxylated, and the glycols or polyglycols have been reacted
with other carboxylic acids or C4-C30 polycarboxylic acids or derivates of carboxylic or polycarboxylic acids.
3. Composition according to claim 1 or 2 wherein
in the component (A) the dicarboxylic anhydride is maleic anhydride and the alpha-olefins
have a chain length of 12 to 30 C-atoms and the base is ammonia, an amine or an alkali
or earth alkali hydroxide in aqueous dispersion with or without solvents,
in the component (B) the dicarboxylic anhydride is maleic anhydride, and the fatty
acids or fatty alcohols or oxo-alcohols have a chain length of 12 to 30 C-atoms and
are ethoxylated/propoxylated with 2- 25 mol of EO/ PO or the fatty acids are reacted
with polyglycols 100 - 1200, and
the component (C) is a reaction product of (B) with sodium bisulphite carried out
in aqueous medium.
4. Composition according to claim 3 wherein
in the component (A) the alpha-olefins have a chain length of 18 to 24 C-atoms and
the base is NaOH,
in the component (B) the fatty acids or fatty alcohols or oxo-alcohols have a chain
length of 12 to 20 C-atoms and have one or more double bonds, and the fatty acids
and fatty alcohols or oxo-alcohols have been ethoxylated.
5. Composition according to claim 4 wherein
in the component (B) the fatty acids have been reacted prior to the reaction with
maleic anhydride with polyethylene glycols or glycols.
6. Composition according to claim 3 or 4 wherein
in the component (A) the alpha-olefins have a chain length of 20 to 22 C-atoms,
in the component (B) the fatty acid is oleic acid and wherein the polyethylene glycol
is a polyethylene glycol of the formula HO(CH2CH2O)nH with an average number of n from 2 to 25.
7. Composition according to any of the preceding claims wherein the molar ratio of (A):[(B)
+ (C)] is from 5:100 to 100:5 and the molar ratio from (B):(C) is from 5:100 to 100:5.
8. Composition according to claim 7 wherein the molar ratio of (A):[(B)+(C)] is from
50:100 to 100:50, and the molar ratio from (B):(C) is from 20:100 to 100:20.
9. Composition according to any of the preceding claims, further comprising amides and
esters of the component (A).
10. Composition according to any of the preceding claims, further comprising at least
one formulation additive (S) selected from
• water or an organic solvent or mixture and/or solubiliser or mixture miscible with
or soluble in (A) and (B) and (C) or in which (A) and (B) and (C) are soluble,
• a defoamer,
• a natural or mineral oil,
• a surfactant,
• a lecithine and
• a biocide.
11. Process for producing a composition according to claim 1 by mixing the components
(A), (B) and (C) and optionally adding any formulation additive (S).
12. Use of a composition according to claims 1 to 10 for retanning and fatliquoring of
pelts, skins, hides, leather intermediate products or non-finished leather.
13. A process for retanning or fatliquoring of pelts, skins, hides, leather intermediate
products or non-finished leather comprising a treatment with a composition according
to any of claims 1 to 10.
1. Zusammensetzung, umfassend die Bestandteile (A), (B) und (C), wobei
(A) ein Produkt der Umsetzung eines ethylenisch ungesättigten C4-C8-Dicarbonsäureanhydrids mit C3-C40-alpha-Olefinen mit anschließender teilweiser oder vollständiger Neutralisierung mit
einer Base ist, in einer wässrigen Dispersion mit oder ohne Lösemittel,
(B) ein Produkt der Umsetzung von ethylenisch ungesättigten C4-C8-Dicarbonsäureanhydriden mit C10-C40-Fettsäuren oder C4-C30-Polycarbonsäuren oder C10-C40-Fettalkoholen oder Oxoalkholen oder Glykolen oder Polyglykolen oder C3-C20 organischen Aminen ist, wobei alle diese gesättigt oder ungesättigt, geradkettig
oder verzweigt sein können und die Fettsäuren ethoxyliert und/oder propoxyliert sind
oder mit Polyglykolen oder Glykolen umgesetzt wurden, und wobei die Polycarbonsäuren
ethoxyliert und/oder propoxyliert sind oder mit Polyglykolen oder Glykolen umgesetzt
wurden, was zumindest eine ihrer Carbonsäuregruppen betrifft, während die Fettalkohole
oder Oxoalkohole und die Fettamine möglicherweise ethoxyliert und/oder propoxyliert
sein können, und
(C) ein Produkt der Reaktion von (B) mit Bisulfit oder Metabisulfit oder Sulfit oder
Schwefelsäure oder rauchender Schwefelsäure ist, welches anschließend mit einer Base
teilweise oder vollständig neutralisiert wird, wobei es sich bei der Base um ein Alkali-
oder Erdalkalihydroxid, Ammoniak oder ein organisches Amin in wässriger Dispersion
mit oder ohne Lösemittel handelt.
2. Zusammensetzung gemäß Anspruch 1, wobei
im Bestandteil (A) ein Teil der Anhydridgruppen mit Alkoholen, Polyalkoholen, Glykolen
oder organischen Aminen oder Ammoniak umgesetzt wird
im Bestandteil (B) die Fettalkohole oder Oxoalkohole und die Fettamin ethoxyliert
und/oder propoxyliert wurden, und die Glykole oder Polyglykole mit weiteren Carbonsäuren
oder C4-C30-Polycarbonsäuren oder Derivaten von Carbon- oder Polycarbonsäuren umgesetzt wurden.
3. Zusammensetzung gemäß Anspruch 1 oder 2, wobei
im Bestandteil (A) das Dicarbonsäureanhydrid gleich Maleinsäureanhydrid ist und die
alpha-Olefine eine Kettenlänge von 12 bis 30 C-Atomen aufweisen und es sich bei der
Base um Ammoniak, ein Amin oder ein Alkali- oder Erdalkalihydroxid in wässriger Dispersion
mit oder ohne Lösemittel handelt,
im Bestandteil (B) das Dicarbonsäureanhydrid gleich Maleinsäureanhydrid ist, und die
Fettsäuren oder Fettalkohole oder Oxoalkohole eine Kettenlänge von 12 bis 30 C-Atomen
aufweisen, wobei sie mit 2 bis 25 Mol an EO/PO ethoxyliert/propoxyliert sind, oder
die Fettsäuren mit Polyglykolen 100 - 1200 umgesetzt werden, und
der Bestandteil (C) ein Produkt der Umsetzung von (B) mit Natriumbisulfit ist, wobei
diese im wässrigen Milieu durchgeführt wird.
4. Zusammensetzung gemäß Anspruch 3, wobei
im Bestandteil (A) die alpha-Olefine eine Kettenlänge von 18 bis 24 C-Atomen aufweisen
und die Base gleich NaOH ist,
Im Bestandteil (B) die Fettsäuren oder Fettalkohole oder Oxoalkohole eine Kettenlänge
von 12 bis 20 C-Atomen aufweisen und eine oder mehrere Doppelbindungen haben, und
die Fettsäuren und Fettalkohole oder Oxoalkohole ethoxyliert wurden.
5. Zusammensetzung gemäß Anspruch 4, wobei
im Bestandteil (B) die Fettsäuren, im Vorfeld der Reaktion mit Maleinsäureanhydrid,
mit Polyethylenglykolen oder Glykolen umgesetzt wurden.
6. Zusammensetzung gemäß Anspruch 3 oder 4, wobei
im Bestandteil (A) die alpha-Olefine eine Kettenlänge von 20 bis 22 C-Atomen haben,
im Bestandteil (B) die Fettsäure gleich Ölsäure ist, und wobei das Polyethylenglykol
ein Polyethylenglykol mit der Formel HO(CH2CH2O)nH ist, dessen Anzahl an n im Durchschnitt 2 bis 25 beträgt.
7. Zusammensetzung gemäß einem beliebigen der vorhergehenden Ansprüche, wobei das Molverhältnis
von (A):[(B)+(C)] im Bereich von 5:100 bis 100:5 liegt und das Molverhältnis von (B):(C)
im Bereich von 5:100 bis 100:5 liegt.
8. Zusammensetzung gemäß Anspruch 7, wobei das Molverhältnis von (A):[(B)+(C)] im Bereich
von 50:100 bis 100:50 liegt und das Molverhältnis von (B):(C) im Bereich von 20:100
bis 100:20 liegt.
9. Zusammensetzung gemäß einem beliebigen der vorhergehenden Ansprüche, die weiterhin
Amide und Ester des Bestandteils (A) umfasst.
10. Zusammensetzung gemäß einem beliebigen der vorhergehenden Ansprüche, die weiterhin
mindestens einen Formulierungshilfsstoff (S) umfasst, welcher aus den folgenden ausgewählt
ist
• Wasser oder einem organischen Lösemittel oder Mischung und/oder Löslichkeitsvermittler
oder Mischung, welches/welche mit (A) und (B) und (C) mischbar oder darin löslich
ist, oder in welchem (A) und (B) und (C) löslich sind,
• einem Schaumverhüter,
• einem natürlichen oder mineralischen Öl,
• einem Tensid,
• einem Lecithin und
• einem Biozid.
11. Verfahren zur Herstellung einer Zusammensetzung gemäß Anspruch 1, indem die Bestandteile
(A), (B) und (C) vermischt werden und möglicherweise ein beliebiger Formulierungshilfsstoff
(S) zugesetzt wird.
12. Verwendung einer Zusammensetzung gemäß den Ansprüchen 1 bis 10 zum Nachgerben und
Fetten von Pelzen, Häuten, Fellen, Lederzwischenprodukten oder unveredeltem Leder.
13. Verfahren zum Nachgerben oder Fetten von Pelzen, Häuten, Fellen, Lederzwischenprodukten
oder unveredeltem Leder, welches eine Behandlung mit einer Zusammensetzung gemäß einem
beliebigen der Ansprüche 1 bis 10 umfasst.
1. Composition comprenant les composants (A), (B) et (C) dans laquelle
(A) est un produit de réaction d'un anhydride dicarboxylique en C4-C8 à insaturation éthylénique avec des alpha-oléfines en C3-C40 suivie d'une neutralisation partielle ou totale avec une base, en dispersion aqueuse
avec ou sans solvants,
(B) est un produit de réaction d'anhydrides dicarboxyliques en C4-C8 à insaturation éthylénique avec des acides gras en C10-C40 ou des acides polycarboxyliques en C4-C30 ou des alcools gras en C10-C40 ou des oxo-alcools ou des glycols ou des polyglycols ou des amines organiques en
C3-C20, tous étant saturés ou insaturés, linéaires ou ramifiés et les acides gras étant
éthoxylés et/ou propoxylés ou ayant été amenés à réagir avec des polyglycols ou des
glycols et les acides polycarboxyliques étant éthoxylés et/ou propoxylés ou ayant
été amenés à réagir avec des polyglycols ou des glycols au moins avec un groupe carboxylique
et les alcools gras ou oxo-alcools et les amines grasses pouvant facultativement être
éthoxylés et/ou propoxylés,
(C) est un produit de réaction de (B) avec un bisulfite ou un métabisulfite ou un
sulfite ou de l'acide sulfurique ou de l'oléum, suivie d'une neutralisation partielle
ou totale avec une base, la base étant un hydroxyde de métal alcalin ou alcalinoterreux,
l'ammoniac ou une amine organique en dispersion aqueuse avec ou sans solvants.
2. Composition selon la revendication 1 dans laquelle
dans le composant (A) une partie des groupes anhydrides sont amenés à réagir avec
des alcools, des polyols, des glycols ou des amines organique ou de l'ammoniac et
dans le composant (B) les alcools gras ou oxo-alcools et les amines grasses ont été
éthoxylés et/ou propoxylés et les glycols ou polyglycols ont été amenés à réagir avec
d'autres acides carboxyliques ou des acides polycarboxyliques en C4-C30 ou des dérivés d'acides carboxyliques ou polycarboxyliques.
3. Composition selon la revendication 1 ou 2 dans laquelle
dans le composant (A) l'anhydride dicarboxylique est l'anhydride maléique et les alpha-oléfines
ont une longueur de chaîne de 12 à 30 atomes de carbone et la base est l'ammoniac,
une amine ou un hydroxyde de métal alcalin ou alcalinoterreux en dispersion aqueuse
avec ou sans solvants,
dans le composant (B) l'anhydride dicarboxylique est l'anhydride maléique et les acides
gras ou alcools gras ou oxo-alcools ont une longueur de chaîne de 12 à 30 atomes de
carbone et sont éthoxylés/propoxylés avec 2-25 mol d'OE/OP ou les acides gras sont
amenés à réagir avec des polyglycols 100-1200 et
le composant (C) est un produit de réaction de (B) avec du bisulfite de sodium effectuée
en milieu aqueux.
4. Composition selon la revendication 3 dans laquelle
dans le composant (A) les alpha-oléfines ont une longueur de chaîne de 18 à 24 atomes
de carbone et la base est NaOH,
dans le composant (B) les acides gras ou alcools gras ou oxo-alcools ont une longueur
de chaîne de 12 à 20 atomes de carbone et une ou plusieurs doubles liaisons et les
acides gras et alcools gras ou oxo-alcools ont été éthoxylés.
5. Composition selon la revendication 4 dans laquelle
dans le composant (B) les acides gras ont été amenés à réagir avant la réaction avec
de l'anhydride maléique avec des polyéthylèneglycols ou des glycols.
6. Composition selon la revendication 3 ou 4 dans laquelle
dans le composant (A) les alpha-oléfines ont une longueur de chaîne de 20 à 22 atomes
de carbone,
dans le composant (B) l'acide gras est l'acide oléique, le polyéthylèneglycol étant
un polyéthylèneglycol représenté par la formule HO(CH2CH2O)nH ayant un nombre moyen n de 2 à 25.
7. Composition selon l'une quelconque des revendications précédentes dans laquelle le
rapport molaire de (A):[(B) + (C)] est de 5:100 à 100:5 et le rapport molaire de (B):(C)
est de 5:100 à 100:5.
8. Composition selon la revendication 7 dans laquelle le rapport molaire de (A):[(B)
+ (C)] est de 50:100 à 100:50 et le rapport molaire de (B):(C) est de 20:100 à 100:20.
9. Composition selon l'une quelconque des revendications précédentes, comprenant en outre
des amides et des esters du composant (A).
10. Composition selon l'une quelconque des revendications précédentes, comprenant en outre
au moins un additif de formulation (S) choisi parmi
- l'eau ou un solvant organique ou un mélange et/ou un agent solubilisant ou un mélange
miscibles avec (A) et (B) et (C) ou solubles dans (A) et (B) et (C) ou dans lesquels
(A) et (B) et (C) sont solubles,
- un antimousse,
- une huile naturelle ou minérale,
- un tensioactif,
- une lécithine et
- un biocide.
11. Procédé pour la production d'une composition selon la revendication 1 par mélange
des composants (A), (B) et (C) et facultativement ajout de tout additif de formulation
(S).
12. Utilisation d'une composition selon les revendications 1 à 10 pour le retannage et
la nourriture en bain de cuirs en tripe, de peaux, de cuirs bruts, de produits intermédiaires
du cuir ou de cuir non fini.
13. Procédé pour le retannage ou la nourriture en bain de cuirs en tripe, de peaux, de
cuirs bruts, de produits intermédiaires du cuir ou de cuir non fini comprenant un
traitement avec une composition selon l'une quelconque des revendications 1 à 10.