BRPI0819700B1 - Leather Retanning and Lubricating Composition, Production Process and Use - Google Patents

Abstract

Leather Retanning and Lubricating Agent The present invention relates to a wet and lubricating retanning composition of skins, hides, hides, intermediate leather or unfinished leather consisting of (a) a reaction product of an ethylenically unsaturated C4-C8 dicarboxylic anhydride with C3-C40 alpha-olefins, followed by partial or total neutralization with a base, (8) a reaction product of ethylenically unsaturated cacs-C10-C40 fatty acids or C4 -C30 polycarboxylic acids or C1 -C40 fatty alcohols or oxoalcools or C3 -C20 organic glycols or polyglycols or amines, all being saturated or unsaturated, linear or branched and the fatty acids being ethoxylated and / or propoxylated and / or having reacted with polyglycols or glycols, and the c4-c30 polycarboxylic acids being ethoxylated and / or propoxylated and / or having reacted with polyglycols or glycols with at least one carboxylic group, and (c) a reaction product of (b) with bisulfite or metabisulfite or sulfite or sulfuric acid or oil preferably neutralized with a base, wherein the base is an alkali or alkaline earth metal hydroxide, ammonia or an organic amine.

Description

[001] The present invention relates to a composition for wet retanning and the greasing of hair, skins, hides, intermediate leather or unfinished leather products and their production and use.

[002] For wet retanning and greasing, the leather industry is using different compounds, in particular polymeric compounds have been proposed to obtain smooth and firm leather types.

[003] US Patent 5,279,613 discloses copolymers that are obtainable by free radical copolymerization of (a) mono-olefins-CeC40 with (b) ethylenically unsaturated C4-C8 dicarboxylic anhydrides by mass polymerization from 80 ° C to 300 ° C ° C to produce copolymers having molecular weights from 500 to 20,000 g / mol, with subsequent solvolysis of the anhydride groups of the copolymers and partial or complete neutralization of the carboxylic groups formed during solvolysis, in an aqueous medium by means of a base, and which it is present in the form of aqueous dispersions or solutions, being used as agents to produce impermeable leathers and hides.

[004] US Patent 5,575,939 discloses a process for greasing / softening leather and hair, by treating with an aqueous dispersion of a copolymer achievable by the polymerization of a) maleic anhydride, b) alpha-olefins-C2-C3o, esters of (meth) acrylic acid and / or maleic acid with C1 -C3 alcohol C) and c) optionally, also ethylenically unsaturated hydrophilic monomers being 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 the production of a flowable dispersion having a

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2/28 active substance content of at least 40% by weight.

[005] However, there is always a need for compounds with even better properties.

[006] It has now been surprisingly found that with the composition defined below, an exceptional and highly satisfactory retanning and greasing of substrates can be achieved in wet retanning and in the greasing of hair, skins, leathers, intermediate leather or unfinished leather. .

[007] Therefore, an object of the present immediate invention is a composition consisting of components (A), (B) and (C) in which:

(A) is a product of the reaction of an ethylenically unsaturated dicarboxylic anhydride-C4Ce with alpha-olefins-C3-C4o, used in the acid form or preferably followed by partial or total neutralization with a base in an aqueous dispersion with or without solvents, optionally the part of the anhydride groups is reacted with alcohols, polyalcohols, glycols or organic amines, (B) is a product of the reaction of ethylenically unsaturated dicarboxylic anhydride-C4-C4o fatty acids or C4-C3o polycarboxylic acids or alcohols fatty-Cio-C4o or oxoalcohols or glycols or polyglycols or organic amines-C3-C2o, all being saturated or unsaturated, linear or branched and the fatty acids being ethoxylated and / or propoxylated or having reacted with polyglycols or glycols, and polycarboxylic acids being ethoxylated and / or propoxylated or having reacted with polyglycols or glycols with at least one carboxylic group, while fatty alcohols or oxoalcohols and amines g ratios can optionally be ethoxylated and / or propoxylated, and (C) is a product of the reaction of (B) with bisulfite or metabisulfite or sulfite or sulfuric acid or oil preferably neutralized with a base where the base is an alkali or alkaline earth metal hydroxide , ammonia or an organic amine in a dispersion

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3/28 aqueous with or without solvents.

[008] In component (B), glycols or polyglycols can be reacted with other carboxylic acids or C4-C3o polycarboxylic acids or derivatives of carboxylic or polycarboxylic acids.

[009] This composition provides excellent softening and retanning properties that can make additional treatment with retanning and unnecessary lubricating agents. It gives leather exceptional chemical and physical properties: excellent fogging values, good luminosity and heat stability, without purging problems, ecological advantage: low COD in the bath, no phenol or formaldehyde in the bath as well as leather (normally present in baths and leathers after treatments with common retanning agents), properties that are otherwise very difficult to achieve with the standard greasing and retanning agents already available on the market.

[0010] Preferred are compositions in which:

in component (A), dicarboxylic anhydride is maleic anhydride and alpha-olefins have a chain length of 12 to 30 carbon atoms and the base is ammonia, an amine or an alkali or alkaline earth metal hydroxide in an aqueous dispersion with or without solvents, in component (B), dicarboxylic anhydride is maleic anhydride, and fatty acids or fatty alcohols or oxoalcohols have a chain length of 12 to 30 carbon atoms and are ethoxylated / propoxylated with 2 to 25 rols EO / PO (ethylene oxide / propylene oxide) or fatty acids are reacted with polyglycols 100 1200, component (C) is a product of the reaction of (B) with sodium bisulfite carried out in an aqueous dispersion.

[0011] Particularly good properties are shown by

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4/28 compositions in which in component (A), alpha-olefins have a chain length of 18 to 24 carbon atoms and the base is NaOH, in component (B), fatty acids or fatty alcohols or oxoalcohols have a chain length of 12 to 20 carbon atoms and have one or more double bonds, and the fatty acids and fatty alcohols or oxoalcohols have been ethoxylated and optionally the fatty acids have been reacted with polyethylene glycol or glycols before reaction with maleic anhydride.

[0012] Examples of said fatty acids used for (B) are lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, or alpha-linolenic acid. Preferred are oleic acid and linoleic acid or mixtures thereof, and oleic acid is particularly preferred.

[0013] Preferred examples of said alcohols used for (B) are oleyl alcohol, linoleyl alcohol, cetyloleyl alcohols or mixtures thereof as well as branched alcohols from oxosynthesis such as Cg, C-io, C11, C12, C13 - Cu oxoalcools, C15 or mixtures thereof.

[0014] Particularly preferred compositions are those in which in component (A), alpha-olefins have a chain length of 20 to 22 carbon atoms, in component (Β), fatty acid is oleic acid and in that polyethylene glycol is a polyethylene glycol according to the formula HO (CH2CH2O) _n H with an average number n from 2 to 25 (eg polyglycols 100-1200).

[0015] The alpha-olefins used are commercial products. A chain length of 20 to 22 carbon atoms does not exclude smaller amounts (up to 10 mol%) of Cie or shorter and C24 or longer.

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5/28 [0016] The oleic acid used is a commercial product from natural sources, which means the mixture of C12-C18 fatty acids while the percentage of oleic acid is> 60%.

[0017] Immediate compositions, in general, have a molar ratio of (A): [(B) + (C)] from 5: 100 to 100: 5 and a molar ratio of (B): (C) of 5 : 100 to 100: 5.

Preferred are compositions in which the molar ratio of (A): [(B) + (C)] is 50: 100 to 100: 50, more preferably 70: 100 to 100: 70 and the molar ratio of (B) :( C) is 20: 100 to 100: 20, more preferably 60: 100 to 100: 60.

[0019] The immediate compositions can also comprise amides and esters of (A) as described in US Patent 5,279,613. The details of these amidation and esterification reactions are found in this prior art.

[0020] The immediate compositions can also comprise at least one formulation additive (S), for example, to adjust the physical aspect of the composition and / or its usage properties and can be selected from water or an organic solvent or a solubilizer 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. Also at least one of the following additives or mixtures thereof can be contained: defoamers, natural or mineral oils, surfactants, lecithins, biocides.

(S) may in particular comprise one or more solvents and / or solubilizers 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 a mixture of organic solvents and / or a solubilizer or mixture of solubilizers, miscible with or soluble in (A) and (B) and ( C) or where (A) and (B) and (C) are soluble, (S3) a defoamer

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6/28 and / or (S4) a surfactant and / or (S5) a mineral or natural oil and / or (S6) synthetic or natural lecithin and / or (S7) a biocide.

[0021] Preferably (S2) is a water-miscible organic solvent, which is aliphatic and contains at least one oxygen and no other heteroatom, or a mixture of two or more of such solvents. More preferably (S2) is selected from the group consisting of mono or oligofunctional aliphatic alcohols and mono- or di- (C 1 -C 4 -alkyl) ethers. (S2) can include water-miscible saturated aliphatic solvents of an alcohol and / or ether character. As (S2), in particular, a C3-C4 alkanol, a diol which is a C2-C4 alkylene glycol or a higher diol, for example, with 6 carbon atoms mainly 2-methyl-2,4-pentanediol (hexylene glycol), dipropylene glycol or a di or tri or tetraethylene glycol, and mono or (C 1 -C 4 -alkyl) ethers thereof, or glycerol. Particularly preferred solvents or solubilizers (S2) include, for example: isopropanol, mono or dipropylene glycol, mono, di, tri or tetraethylene glycol, hexylene glycol, monomethylether mono or dipropylene glycol, ethylene monobutylether and methyl, ethyl, isopropyl or butyl mono- or diethers of di, tri or tetraethylene glycol.

[0022] As solvents / solubilizers in (S) water (S1) alone, solvent or solubilization (S2) alone or a mixture of water (SI) and solvent or solubilization (S2) can be used.

[0023] As defoamers (S3), known products can be used in commercially available forms, such as, for example, silicones, silica, paraffin, paraffin oil, mineral oil or trialkyl phosphates (for example, triisopropyl phosphate or phosphate of tributyl), ethers, alkoxylated fatty esters, alkoxylated fatty acids, in an efficient concentration, for example, below 0.2% by weight, preferably below 0.1% by weight, based on the dry amount of (A) + (B) + (C). Especially a defoamer (S3) is not

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7/28 required and is not added.

[0024] As a surfactant (S4) any conventional nonionic or anionic surfactant can be used in particular with an emulsifying character.

[0025] As nonionic surfactants, alkoxylated alcohols, mainly ethoxylated, are preferably used. As alkoxylated alcohols, some alkoxylates may also be used, preferably ethoxylated oxoalcohols.

[0026] As an anionic surfactant, emulsifiers preferably contain a sulfo group, optionally a phosphorus group. Preferably as an anionic surfactant (S4), arylaliphatic sulphate is used or more preferably aliphatic sulphate, which can contain a heteroatomic bridge in the aliphatic chain (for example, ester, amine, amide or preferably an ether bridge) and which contains a lipophilic hydrocarbon radical, for example, with 7 to 24 carbon atoms, more preferably sulfuric acid monoesters of fatty alcohols or ethoxylated fatty alcohols (for example, from mono to ethoxylated oligo) or grease amine with, for example, 12 to 24 carbon atoms in the fatty hydrocarbon radical. Among these, sulfuric acid esters of ethoxylated fatty alcohols are preferred. Optionally as anionic surfactants esters of arylaliphatic mono or diphosphoric acids or more preferably aliphatic or a mixture thereof are employed. Among these, phosphoric acid esters of ethoxylated fatty alcohols are preferred.

[0027] Anionic surfactants (S4) are preferably in the form of alkali metal salts, more preferably potassium or sodium salts.

[0028] As mineral or natural oils (S5), fluid hydrocarbons from petroleum distillation, paraffinic hydrocarbons and / or natural or synthetic waxes or trigliPetição 870190003891, from 01/14/2019, p. 10/40

8/28 plant or animal cerines.

[0029] If it is desired to modify the application properties, synthetic or natural lecithin (S6) can be used. Especially lecithin is not necessary and is not added.

[0030] As a biocide (S7), known products in commercially available forms can be used, for example, biocide based on 1,2-benzoisothiazolinon-3 and 1,2-dibromo-2,4dicianobutane, chlorine or chlorine based biocide free of isothiazolinoni, based on bronopol, based on 2- (thiocyanomethylthio) -benzothiazole or based on p-chloro-m-cresol. These products can be used alone or in a mixture.

[0031] Polymers (A) are basically known products and, for example, are described in US Patent 5,279,613, US Patent 5,575,939 or DE 3730885. Details of their preparation are also disclosed in these documents.

[0032] The immediate compound (B) is not a polymerization product where radical polymerization occurs and therefore still contains double bonds, in contrast to the product of US Patent 5,575,939 where a radical polymerization takes place.

[0033] Component B can be obtained by heating the mentioned starting compounds to a temperature in the range of 80 to 160 ° C, with the distillation of water, if necessary, optionally under vacuum for 2 to 6 hours and in the presence of an organic solvent, if necessary.

[0034] Ethoxylated or ethoxylated products and propoxylated products (fatty acids, fatty alcohols, oxoalcohols) are known or can be produced in a normally conventional manner, by the reaction of adding ethylene oxide or ethylene oxide and propylene oxide mixtures of fatty acids, fatty alcohols, oxoalcohols, or organic amines.

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9/28 [0035] Ethoxylation means here the reaction of adding ethylene oxide (also known as oxyethylation). Propoxylation here means the reaction of adding propylene oxide (also known as oxypropylation).

[0036] The addition reaction can be carried out under reaction conditions known per se, preferably in the presence of an alkali metal hydroxide, for example, sodium hydroxide or potassium hydroxide, with heating, for example, at a temperature in the range ranging from 90 to 240 ° C, preferably 130 to 220 ° C in a closed vessel, in the presence of an inert gas, for example, nitrogen. If the propylene oxide is also reacted, it is preferably reacted first, followed by the ethylene oxide reaction. Propylene oxide, if used, is used in a smaller proportion, preferably in this case that 1 to 2 mois of propylene oxide is added per mole of fatty acids or fatty alcohols or oxoalcoholes or mixture of organic amines; more preferably no propylene oxide is added, but the mixture of fatty acids or fatty alcohols or oxoalcohols or organic amines is reacted only with ethylene oxide. The molar proportion of ethylene oxide referred to fatty acids or fatty alcohols or oxoalcohols or organic amines or mixtures thereof is in the range of 2 to 25, preferably 6 to 14.

[0037] The reaction of fatty acids with polyglycols can be carried out at a temperature in the range of 80 to 160 ° C for 2 to 6 hours optionally under vacuum (such as, for example, from 50 to 70 mm Hg), preferably with an acid catalyst like methanesulfonic acid, as an example.

[0038] The parts of component (B) are also reacted to synthesize (C) with sodium bisulfite at a temperature in the range of 60 to 120 ° C for 2 to 10 hours in the presence of water,

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10/28 alkaline earth metal hydroxide and, if necessary, organic solvents (such as, for example, 2-propanol). The preferred pH range during the reaction is 5 to 8.

[0039] The compositions of the present invention can be produced in a normally conventional manner, for example, by mixing components (A), (B) and (C) and any formulation additive (S).

[0040] Mixtures of (A) with (B) and (C) and any (S) can be carried out, for example, at a temperature in the range of 15 to 70 ° C.

[0041] More preferably the corresponding mixture of (B) and (C) is prepared in a reactor with the necessary addition of sulfite or bisulfite reagent or sulfuric acid or oil to (B) and follows 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.

[0042] 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 at 70 ° C.

[0043] It is also possible to add the mixture of (B) and (C) to component (A) and then (S) is added, if desired, by mixing all components at a temperature in the range of 15 to 70 ° C .

[0044] The compositions thus produced are ready for use. They are of satisfactory stability, storage and transport. They are readily soluble in water which results in an aqueous dispersion and can, for example, be directly dosed in the treatment bath.

[0045] The aqueous dispersions thus obtained are stable and have

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11/28 a long service life. They are very suitable for treating hides and skins because they have a particularly pronounced greasing and retanning action. In many cases, no additional greasing agents based on natural or synthetic greasing oils are required. The dispersions impart a good body and a high tensile strength and tear strength to the product, so that additional treatment with commercial tanning agents, for example, with vegetable tanning agents or synthetic organic tanning agents (sintanos) based on condensed phenolsulfonic acid / phenol / formaldehyde, is no longer needed in most cases.

[0046] The dispersions described above are suitable for the treatment of all conventional tanning of raw hides, in particular tanning of hides with mineral tanning reagents, such as chromium (III) salts.

[0047] The present invention also provides a process of moist retanning and greasing of tanned hair, skins, hides, intermediate products of leather or unfinished leather (crusted leather) or hides, characterized by the fact that such a composition defined above is used as a greasing and retanning agent.

[0048] In particular, the present invention provides a process for the production of leather, fur or fur with fur, comprising in its production at least a wet degreasing treatment, a tanning, a retanning, a greasing and a dyeing or finishing treatment , in which retanning and greasing can be carried out in one step with the immediate composition or completed, if desired, with other commercial greasing and retanning products.

[0049] As a substrate according to the present invention any products of raw leather, skins or pelizos as conventionally processed in the river, tanned with

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12/28 on a regular basis to purchase wet blue or wet white leathers. For example, fur, hides or cow hides, sheep, goats, pigs, cattle and other animals (eg horse, foal, reptiles, eg snake, lizards, water reptiles, doe, deer) may be mentioned , ostrich, poultry, dromedary, camel and camel-like animals, for example, mud or alpaca), and woolly skins (mainly sheep or goats) and fur.

[0050] Retanning and greasing according to the present invention can also be applied to intermediate leather products or unfinished leather (leather with crust). Thus, if the substrate has already been tanned or retanned, the immediate composition can be used before dyeing, especially to improve the dispersion capacity of the dye, for example, dispersion and uniform distribution of the dye, or after dyeing to give a more dye full-bodied and deeper, or before finishing to prepare the substrate for a particular uniform finish connection.

[0051] For the retanning and greasing bath, for example, one or more anionic surfactants (G) and / or a water-miscible solvent (H) may be added.

[0052] As anionic surfactants (G) any conventional surfactants can be used, preferably those containing a sulfo group, for example, aliphatic or arylaliphatic sulfates (G1) or sulfonates (G2), which may contain a heteroatomic bridge in the chain aliphatic (for example, an ester, ether or preferably amide bridge, an ether bridge which is with a preferably preferred part of a glycol ether chain) and which contains a lipophilic hydrocarbon radical, for example, from 7 to 24 carbon atoms. They are preferably in the form of alkali metal salts, more preferably potassium or sodium salts.

[0053] Suitable sulphates (G1) are, for example:

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13/28 (GT) sulfuric acid monoesters of fatty alcohols or ethoxylated fatty alcohols (eg mono to oligoethoxylated) or grease amine with eg 12 to 24 carbon atoms in the fatty hydrocarbon radical, (G1) acid esters sulfuric fatty acid monoglycerides with, for example, 12 to 24 carbon atoms in the fatty acid radical, (GT) unsaturated fatty acid sulphation products or unsaturated oils (fatty acid triglycerides) with, for example, 18 to 22 atoms of carbon in the radical unsaturated fatty acid or of ricinoleic acid or castor oil.

[0054] Suitable sulphonates (G2) are, for example:

(G2 ') fatty alkyl sulfonates and isothionates, with, for example, 12 to 24 carbon atoms in the fatty hydrocarbon radical, petroleum sulfonate (mainly secondary sulfonates with, for example, 10 to 15, usually 12 to 13, carbon atoms) carbon in the aliphatic chain), (G2) taurides and N-methyltaurides of fatty acid with, for example, 12 to 24 carbon atoms in the fatty acid radical, (G2 ') sulfation products of unsaturated fatty acids or unsaturated oils (triglycerides of fatty acid) with, for example, 16 to 24 carbon atoms in the radical unsaturated fatty acid, (G2) mono and dialkyl benzene sulfonates with, for example, a total of 1 to 12 carbon atoms in the substitution of alkyl, for example, with 4 to 12 carbon atoms in the alkyl chain, or short-chain alkylbenzene sulfonate with 1 to 3 carbon atoms in the alkyl radical and in the total alkyl substitution.

[0055] As mono to oligoethoxylated in (GT) is meant the product of adding 1 to 10 moles of ethylene oxide to one mole of fatty alcohol. As the examples of (G1) can be mentioned in

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14/28 determined lauryl sulphate, stearyl sulphate, and sulphates from the addition product of 1 to 6 moieties of ethylene oxide to one mole of stearyl or lauryl alcohol. As the examples of (G2) can be mentioned in particular in toluene, xylene or cumene sulfonic acid, and taurid fatty acids or N-methyl taurides with, on average, from 16 to 20 carbon atoms in the fatty acid radical. They are preferably in the form of potassium salts or more preferably sodium salts. [0056] The solvents (H) are water miscible, organic, preferably aliphatic solvents that contain at least two oxygen atoms linked per molecule in the form of alcoholic hydroxy groups and / or ether bridges, and are in particular free of other heteroatoms different from oxygen. Particular mention may be made of compounds with a saturated ether and / or aliphatic alcohol character, mainly mono, di, tri and / or tetraalkylene glycols and their mono or di (C1-4 alkyl) ethers, preferably with> 4 carbon atoms in the molecule, more preferably with> 6 carbon atoms, for example, 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- or di- or triethylene glycol, among which monoalkyl ethers are preferred, in particular diethylene glycol monobutyl ether.

[0057] According to a characteristic of the present invention, one or more anionic surfactants (G) and / or a water miscible solvent (H) can be added in the immediate composition.

[0058] Wet retanning and greasing with immediate composition can be carried out analogously to methods already known, opportunely in a treatment drum or in a rotating water bath, for example, in the range of 3 to 100%, preferably 5 to 40%, more preferably 5 to 15% by weight in relation to the wet weight of the tanned leather substrate (wet blue or wet white leather) and the dry weight of the covered leather substrate

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15/28 crust.

[0059] The temperature T of the retanning and the greasing bath is advantageously in the range of 20 to 60 ° C, preferably 30 to 60 ° C. The pH can be as desired and advantageously is in the range of 3.0 to 6.5.

[0060] Retanning and greasing can be carried out in one or more steps, and in each step it can be carried out in one or more steps, preferably two, even if one is already sufficient to acquire good penetration and a homogeneous dispersion of the agents. If carried out in two stages, one stage can be considered as the main stage of retanning and greasing, while the second stage can be considered as a later stage to improve the effects and properties of the substrate.

[0061] According to a characteristic of the invention, the immediate composition can be used alone or if desired in the presence of one or more new tanners or other fat-burning products especially if the leather is produced to purchase certain articles, such as leather from leather articles. car lining.

[0062] According to a feature of the present invention, at least a part of said composition can be combined with other retanning or fat-burning products. Preferably, however, some or at least the required major proportion of other retanning or fattening agents is added separately to the bath, as desired and as appropriate in the stage and / or treatment stage in question.

[0063] For retanning and greasing of tanned substrates, it is advantageous to use for placing the bath and also to rinse from 100 to 400% of water and an organic acid such as formic acid, acetic acid, etc., for example, of a concentration varying from 0.1 to 5%, preferably 0.1 to 0.5% by weight and 0.2 to 3.0% of an agent

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16/28 common humidifier (a single component or a formulation) in relation to the wet hairless weight of the substrate.

[0064] As a wetting agent, one or more anionic surfactants and one or more nonionic surfactants can be employed, preferably one of more formulations of these surfactants present on the market for this scope is employed.

[0065] Then, the substrate is drained, the bath is added with water from 50 to 300%, the pH is increased by the addition of conventional bases or buffer salts, such as sodium acetate, sodium formate of 1.0 to 4.0% or 0.5 to 3.0% sodium bicarbonate or other products having neutralizing / buffering properties.

[0066] The bath is drained, again well washed with water from 50 to 400% and drained again.

[0067] The retanning and greasing treatment of the present invention can be carried out for a duration as conventionally for you for retanning and greasing for example, in the range of 1 to 4 hours, preferably 40 to 70 minutes of each treatment step. (in one or two steps).

[0068] For retanning and greasing of crust-covered substrates, it is an advantage to use for bath placement and also to rinse from 200 to 800% water and an organic acid such as formic acid or acetic acid, for example, of a varying concentration 0.2 to 5%, preferably 0.2 to 2.0% by weight and 0.2 to 4.0% of a wetting agent (alone or in the formulation, many of which are available on the market) in relation to the dry weight of the substrate.

[0069] As a wetting agent, one or more anionic surfactants and one or more nonionic surfactants can be used, preferably one of more formulations of these surfactants present on the market is used for this scope.

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17/28 [0070] Then, the substrate is drained, the bath is added with water from 100 to 600%, the pH is increased by adding conventional bases or buffer salts, such as sodium acetate, sodium formate of 2.0 to 8.0% or sodium bicarbonate from 1.0 to 6.0% or other products having neutralizing / buffering properties.

[0071] The substrate is drained, again thoroughly washed with water from 100 to 800% and drained again.

[0072] The retanning and greasing treatment of the present invention can be carried out for a duration as normally conventional for retanning and greasing, for example, in the range of 1 to 4 hours, preferably 40 to 70 minutes of each treatment step. (in one or two steps).

[0073] After carrying out the retanning and greasing treatment, which is preferably followed by pH adjustments or washing, the substrate can also be directly processed in the expected sequence of treatments of the leather or fur production as desired. If desired, retanning and greasing substrates can even be washed, consequently added with biocides, drained and dried, to be, for example, stored or shipped to be treated in a later stage. Preferably, however, the treatment sequence is not interrupted after retanning and greasing, but the substrate is also treated in the same apparatus. The retanned and greased substrates according to the present invention are readily and optimally suitable for each of the subsequent treatments.

[0074] By the process of the present invention an exceptional degree of retanning and greasing of the substrate can be carried out at the same time. In particular, surprisingly good retanning and greasing can be carried out without damaging other properties.

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18/28 characteristics of the substrate, such as the quality of the leather structure (in particular, the grain structure), handling, dyeing, smooth trim, gentle heating, blurring of the finished leather while subsequent treatment with any chemical finds in the substrate retanned and greased according to the present invention a substrate of high suitability for even the distribution of applied products, for example, fillers, other (re) tanning agents, dyes, pigments, leather softeners, so that leather and excellent quality, dyed and / or finished fur are obtainable with a high yield of the corresponding applied products.

EXAMPLES [0075] The following examples should explain the present immediate invention in more detail. If not indicated otherwise, parts and percentages are by weight and in Application Examples the percentages refer to the wet weight without substrate hair, if not otherwise indicated. The starting materials used in the Examples and the additives used in the Application Examples with respect to retanning and the greasing agent, are commercially available products. The water used is semi-hard, mild water (maximum hardness of -10.55 to -10 ° C) (13-14 ° F).

[0076] I.U.C. standards mentioned in the Application Examples are international standards in leather testing as recommended by IULTCS (International Union of Leather Technologists and Chemical Societies)

PREPARATION EXAMPLES

EXAMPLE 1 [0077] 196 g of oleic acid are loaded into a reactor and, with stirring, 139.0 g of polyglycol 200 are added and 1.3 g of acid

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19/28 methanesulfonic are added. The mixture is heated to 90 105 ° C under vacuum (residual pressure of 50-70 mm Hg in the reactor) and maintained at that temperature for 3-4 hours by distilling water (water to be distilled: 12.5 g).

[0078] 323.8 g. of the reaction mass are cooled to 80-90 ° C and added with 34.1 g. of maleic anhydride. A fragile exothermic reaction takes place. Then, the reaction mass is heated to 88 - 92 ° C and stored at 88 - 92 ° C for 30-40 minutes.

[0079] Then, within 2-3 hours, the mass temperature is raised to 100 - 110 ° C under vacuum (the residual pressure in the reactor is 50-60 mmHg): the condensation water is distilled.

[0080] The reaction mass is then heated to 120 - 130 ° C and stored at 120 - 130 ° C for 2-3 hours, distilling water. Amount of water to be distilled: 6.3 g of water.

Reaction yield: 351.6 g

EXAMPLE 2 [0081] 351.6 g of the product prepared as indicated in example 1 is loaded into the reactor and heated to 80 - 90 ° C and added with an aqueous solution of sodium metabisulfite and NaOH, prepared by mixing 88 parts of water with 33 parts of metabisulfite and 27.5 parts of the 30% NaOH solution.

[0082] The mixture is heated to 85-98 ° C for 2-3 hours. EXAMPLE 3 [0083] 745 g of α-olefin is loaded into a dry reactor and heated to 148-152 ° C. At 140 - 145 ° C, 36 g of di-tert-butylperoxide are added. Then over an hour, 275 g of maleic anhydride, melted at 80-90 ° C, are added under a nitrogen flow and at a temperature of 150-165 ° C. When the addition is complete, the mixture is heated for three hours at 155 - 165 ° C. At the end of the reaction, the polymerization product is poured into a solution

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20/28 aqueous preheated in 80 ° C of 320 g of water and 475 g of the 30% sodium hydroxide solution. The mixture is stirred for one hour at 88-92 ° C and then cooled to 30-35 ° C.

EXAMPLE 4 [0084] 472 g prepared as indicated in example 2 are heated to 40-50 ° C and mixed with 500 g of the product obtained in example 3.

APPLICATION EXAMPLES

EXAMPLE OF APPLICATION A [0085] Retanning and greasing of wet blue cow leather, thickness: 1.5-1.6 mm (percentages are based on hairless weight).

[0086] Wet blue leather (half a leather) is supplied in a drum and 300% water at 40 ° C is added, followed by 0.2% formic acid and the drum is rotated for 15 minutes. The bath is drained. Then 150% water and 2% sodium formate and 1% sodium bicarbonate are added and tipping is continued for 60 minutes at 35-40 ° C. The pH is increased to 5.0. The bath is drained. 200% water at 35 ° C is added and the goods are washed for 10 minutes, after which the bath is drained. 100% water at 40 ° C, 10% of the immediate retanning and lubricating composition are added and the drum is rotated for 60 minutes at this temperature. 0.5% formic acid is added and the drum is rotated for 10 minutes at 40 ° C. Another 0.5% formic acid is added and the drum is rotated for 20 minutes at 40 ° C: the pH is 3.6.

[0087] The bath is drained. 300% water at 25 ° C is added and the goods are washed for 10 minutes, then the bath is drained and the leather is unloaded, assembled and dried using a conventional drying system (selected / positioned / dry at

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21/28 vacuum / hanging dry / conditioning / staked / ventilated), staked to assess the properties of the leather and the lightness, softness to the heat as well as the haze.

[0088] The leather is shortened and greased very regularly, it is firm, tight, smooth and is optimally suited for new processing in the tannery. The light and heat resistances are fine, haze values are excellent.

APPLICATION EXAMPLE B [0089] The retanning and greasing of wet blue cow leather, thickness 1.1-1.2 mm (percentages are based on hairless weight).

[0090] Wet blue leather (half a leather) is supplied in a drum and 300% water at 40 ° C is added, followed by 0.2% formic acid and the drum is rotated for 20 minutes. The bath is drained. Then 100% water, 2% neutralization (like Tanicor AS6), 1.5% of sodium bicarbonate and 3.0% of the immediate composition are added and tipping is continued for 75 minutes at 35 - 40 ° C. The bath is drained. 300% water at 40 ° C is added and the goods are washed for 10 minutes, after which the bath is drained. 100% water at 40 ° C, 3% of the immediate retanning and the lubricating composition are added and tipping is continued for 20 minutes, 3% of a 30% polyacrylate sun (such as Tergotan PR) is added and tipping is continued for 20 minutes, 4.0% phenol / cresol syntane (such as Sandotan SG powder) and 4.0% TARA powder (vegetable tanning agent) are added and tipping is continued for 30 minutes, 3% of Tincture (Melioderm Dark Brown F) is added and tipping is continued for 60 minutes, 0.5% formic acid is added and the drum is rotated for 15 minutes at that temperature, 1.0% formic acid is added and

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22/28 the drum is rotated for 30 minutes at 35-40 ° C.

[0091] The bath is drained. 200% water at 60 ° C is added and the goods are washed for 10 minutes, after which the bath is drained. 150% water is added and 8.0% of the immediate retanning and the lubricating composition is added and the drum is rotated for 60 minutes at 60 ° C. 0.5% formic acid is added and the drum is rotated.

[0092] Afterwards, the bath is drained and the leather is unloaded, worn and dried with one of the conventional drying systems (selected / positioned / vacuum dried / hanging dry / conditioned / staked / ventilated), staked, to evaluate the properties of leather.

[0093] The leather is shortened and greased very regularly, it is firm, tight, very smooth and is optimally suited for new processing in the tannery.

APPLICATION EXAMPLE C [0094] The retanning and greasing of wet blue cow leather, thickness 1.5-1.6 mm (percentages are based on hairless weight).

[0095] Wet blue leather (half a leather) is supplied in a drum and 200% water at 30 ° C is added, followed by 1.0% of a wetting agent (such as Tergolix W 01) and 0.5 % acetic acid and the drum is rotated for 30 minutes. The bath is drained. Then, 50% water at 35 ° C, 5% Baychrom F (basic chromium sulphate) are added and tipping is continued for 90 minutes at 35 - 40 ° C. The leather is left in the bath overnight.

[0096] In the morning, the pH is 3.5. 100% 7 ° B water at 50 ° C and 1% sodium formate are added and the drum is rotated for 30 minutes. The pH is 4.8. The bath is drained. 100% water

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23/28

7 ° Be at 35 ° C, 1% sodium formate is added and rotated for 20 minutes, 1% of sodium bicarbonate is added and rotated for 40 minutes. The pH is 5.6-5.7. The leather is washed with 300% water. The bath is drained. 100% water at 40 ° C, 20% 50% phenol syntane sol (such as Syncotan MRL) are added and drummed for 60 minutes. 1% formic acid is added and the drum is rotated for 20 minutes. The bath is drained.

[0097] 50% water is added at 20 ° C, 1% of the tincture (Bruno Melioderm G) is added and the drum is rotated for 30 minutes. 100% water at 50 ° C, 10% of immediate retanning and greasing composition are added and the drum is rotated for 60 minutes. 1% formic acid is added and the drum is rotated for 20 minutes. The bath is drained.

[0098] 200% water at 15 ° C is added and the drum is rotated for 10 minutes. The bath is drained and the leather is discharged and dried using one of the conventional drying systems (selected / positioned / vacuum dried / hanging dry / conditioned / staked / ventilated), staked, to evaluate the properties of the leather.

[0099] The leather is shortened and greased very regularly, it is firm, tight, smooth and is optimally suited for new processing in the tannery.

Article: Stability to light and heat - greasers Thickness: 1.5 mm

Raw material: wet blue

Method: direct

Origin: LGR

Color: natural

Tanning: chrome% based on: economic weight

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24/28

Date;

Test number: 1201

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25/28

Note Cut: Selected / positioned / vacuum dried / hanging dry / conditioned / staked / airy T Q. 5.0 3.6 Minutes m 09 09 O 20 O O o 40 35 O 40 25 Chemical reagents Water Formic acid Water Sodium formate Sodium bicarbonate Water Composition described above Formic acid Formic acid Water σ ' 300 0.2 150 2.0 O_ 200 100 the o 0.5 0.5 300 Process Washing Drainage Neutralization Drainage Washing Drainage Retanning + + Drainage Washing Drainage Wear

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26/28

Internal costumer

Article: automotive upholstery Thickness: 1.1 to 1.2 mm Raw material: wet blue Method: direct

Origin: LGR

Color: brown

Tanning: chrome% based on: economic weight Date: 07/13/2006

Test number: 1201

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27/28

Note T Q. Minutes 20 75 O 20 20 30 09 in 30 O o 40 40 40 40 Chemical reagents Water Formic acid Water TANICORAS6 Sodium bicarbonate Composition D described above Water Water Composition described above TERGOTAN PR Force SANDOTAN SG Tara Deep Brown Sandoderm F Formic acid Formic acid σ ' 300 0.2 100 2.0 IO 3.0 300 100 3.0 3.0 4.0 4.0 3.0 0.5 0.5 Process Washing Drainage Neutralization + + Drainage Washing Drainage Retanning + + + + + +

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Note Selected / positioned / vacuum dried / conditioned / staked (7 + 7 times by machine) / evaluation / circulated for 24 hours / evaluation T Q. Minutes O 09 30 O O o 09 09 20 Chemical reagents Water Water Composition described above Formic acid Water σ ' 200 150 8.0 0.5 300 Process Drainage Washing Drainage Greasing + Drainage Washing Drainage and loading

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Claims (12)

1. Composition, characterized by the fact that it comprises components (A), (B) and (C), in which: (A) is a product of the reaction of an ethylenically unsaturated C4Ce dicarboxylic anhydride with C3-C40 alpha-olefins followed by partial or total neutralization with a base, in an aqueous dispersion with or without solvents, (B) is a product of the reaction of ethylenically unsaturated dicarboxylic-C4Ce anhydrides with C10-C40 fatty acids or C4-C3o polycarboxylic acids or C1-C4o fatty alcohols or oxoalcohols or glycols or polyglycols or organic amines-C3-C2o all being saturated or unsaturated, linear or branched and linear or branched fatty acids being ethoxylated and / or propoxylated or having reacted with polyglycols or glycols, and polycarboxylic acids being ethoxylated and / or propoxylated or having reacted with polyglycols or glycols with at least one carboxylic group, and (C) is a product of the reaction of (B) with bisulfite or metabisulfite or sulfite or sulfuric acid or oil, followed by partial or total neutralization with a base, where the base is an alkali metal hydroxide alino or alkaline earth, ammonia or an organic amine in an aqueous dispersion with or without solvents. 2. Composition according to claim 1, characterized by the fact that in component (A), a part of the anhydride groups is reacted with alcohols, polyalcohols, glycols or organic amines, or ammonia in component (B), fatty alcohols or oxoalcohols and fatty amines were ethoxylated and / or propoxylated, and the glycols or polyglycols were reacted with other carboxylic acids or C4-C3o polycarboxylic acids or derivatives of carboxylic or polycarboxylic acids. Petition 870190003891, of 01/14/2019, p. 32/40 2/4 Composition according to claim 1 or 2, characterized in that in component (A), the dicarboxylic anhydride is maleic anhydride and alpha-olefins have a chain length of 12 to 30 carbon atoms and the base is ammonia, an alkaline or alkaline earth metal hydroxide in an aqueous dispersion with or without solvents, in component (Β), dicarboxylic anhydride is maleic anhydride, and fatty acids or fatty alcohols or oxoalcohols have a length of chain of 12 to 30 carbon atoms and are ethoxylated / propoxylated with 2 to 25 moles of EO / PO or the fatty acids are reacted with polyglycols 100 to 1200, and component (C) is a product of the reaction of (B) with sodium bisulfite run in an aqueous medium. 4. Composition according to claim 3, characterized by the fact that in component (A), alpha-olefins have a chain length of 18 to 24 carbon atoms and the base is NaOH, in component (B), the fatty acids or fatty alcohols or oxoalcohols have a chain length of 12 to 20 carbon atoms and have one or more double bonds, and fatty acids and fatty alcohols or oxoalcohols have been ethoxylated. 5. Composition according to claim 4, characterized by the fact that, in component (B), the fatty acids were reacted with polyethylene glycol or glycols before the reaction with maleic anhydride. 6. Composition according to claim 3 or 4, characterized in that in component (A), the alpha-olefins have a chain length of 20 to 22 carbon atoms, Petition 870190003891, of 01/14/2019, p. 33/40 3/4 in component (Β), fatty acid is oleic acid and in which polyethylene glycol is a polyethylene glycol according to the formula HO (CH2CH2O) _n H with an average number of n from 2 to 25. The composition according to any one of claims 1 to 6, wherein the molar ratio of (A): [(B) + (C)] is 5: 100 to 100: 5 and the molar ratio of (B) : (C) is from 5: 100 to 100: 5. 8. Composition according to claim 7, characterized by the fact that the molar ratio of (A): [(B) + (C)] is 50: 100 to 100: 50, and the molar ratio of (B) : (C) is 20: 100 to 100: 20. Composition according to any one of claims 1 to 8, characterized in that it still comprises amides and esters of component (A). 10. Composition according to any one of claims 1 to 9, characterized by the fact that it still comprises at least one formulation additive (S) selected from: • water or an organic solvent or the mixture and / or the solubilization or the mixture miscible with or soluble in (A) and (B) and (C) or in which (A) and (B) and (C) are soluble, • a defoamer, • a mineral or natural oil, • a surfactant, • a lecithin and • a biocide. 11. Process for producing a composition as defined in claim 1, characterized in that it is to mix the components (A), (B) and (C) and optionally add any formulation additive (S). 12. Use of a composition as defined in any one of claims 1 to 10, characterized by the fact that it is for retanning and shining of hairs, skins, hides, intermediates