EP2225399A1 - Wiederbräunungs- und fettverflüssigungsmittel für leder - Google Patents

Wiederbräunungs- und fettverflüssigungsmittel für leder

Info

Publication number
EP2225399A1
EP2225399A1 EP08865001A EP08865001A EP2225399A1 EP 2225399 A1 EP2225399 A1 EP 2225399A1 EP 08865001 A EP08865001 A EP 08865001A EP 08865001 A EP08865001 A EP 08865001A EP 2225399 A1 EP2225399 A1 EP 2225399A1
Authority
EP
European Patent Office
Prior art keywords
alcohols
fatty
composition according
component
glycols
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08865001A
Other languages
English (en)
French (fr)
Other versions
EP2225399B1 (de
Inventor
Roberta Gamarino
Licia Trimarco
Michele Giani
Claus Reineking
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Finance BVI Ltd
Original Assignee
Clariant Finance BVI Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant Finance BVI Ltd filed Critical Clariant Finance BVI Ltd
Priority to EP08865001.5A priority Critical patent/EP2225399B1/de
Publication of EP2225399A1 publication Critical patent/EP2225399A1/de
Application granted granted Critical
Publication of EP2225399B1 publication Critical patent/EP2225399B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/28—Multi-step processes

Definitions

  • 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.
  • 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) C12-C30 alpha-olefms, esters of (meth)acrylic acid and/or maleic acid with C12-C30 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.
  • 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 C ⁇ Cs-dicarboxylic anhydride with C3-C4o-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 C ⁇ Cs-dicarboxylic anhydrides with C 10 -C 40 -fatty acids or C4-C30 polycarboxylic acids or C 10 - 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
  • the glycols or polyglycols can be reacted with other carboxylic acids or C4-C30 polycarboxylic acids or derivates of carboxylic or polycarboxylic acids.
  • 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.
  • the component (C) is a reaction product of (B) with sodium bisulphite carried out in aqueous dispersion.
  • 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.
  • 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.
  • 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 C9, Cio, Cn, C 12 , C 13 - C 14 , C 15 oxo-alcohols or mixtures thereof.
  • compositions are those wherein in the component (A) the alpha-olefms 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 2 CH 2 O) n H with an average number of n from 2 to 25 (like for example ,,polyglycol 100 -
  • the alpha-olefms 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.
  • the oleic acid used is a commercial product from natural sources , that means mixture of fatty acids Ci 2 -CiS whereas the percentage of oleic acid is > 60%.
  • 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.
  • 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.
  • 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.
  • 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.
  • formulation additive 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.
  • at least one of the following additives or mixtures thereof may be contained: defoamers, natural or mineral oils, surfactants, lecithines , biocides.
  • (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.
  • (S) is selected from the group comprising (Sl) 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.
  • (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 oligo functional alcohols and mono- or di-(Ci-C4-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 C3-C4-alkanol, a diol which is a C 2 -C 4 -alkylene glycol or a higher diol e.g.
  • Particularly preferred solvents or solubilisers 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.
  • solvents/solubilisers in (S) there may be employed water (Sl) alone, solvent or solubiliser (S2) alone or a mixture of water (Sl) and solvent or solubiliser (S2).
  • 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). Usually a defoamer (S3) is not necessary and is not added.
  • surfactants (S4) there may be employed any conventional non ionic or anionic surfactants in particular with emulsif ⁇ er character.
  • non ionic surfactants are preferably employed alkoxylated, mainly ethoxylated, alcohols.
  • alkoxylated alcohols can also be employed some alkoxylated, preferably ethoxylated oxo-alcohols.
  • anionic surfactant preferably emulsif ⁇ ers contain a sulpho group, optionally a phosphorus group.
  • 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.
  • sulphuric acid esters of ethoxylated fatty alcohols are preferred.
  • anionic surfactant are employed arilaliphatic or more preferably aliphatic mono- or di-phosphoric acid esters or mixture thereof.
  • phosphoric acid esters of ethoxylated fatty alcohols are preferred.
  • the anionic surfactants (S4) are preferably in the form of alkali metal salts, more preferably sodium or potassium salts.
  • mineral or natural oils may be employed hydrocarbons fluid got by distillation of the oil, paraffinic hydrocarbons and / or natural or synthetic waxes or vegetable or animal tryglycerides.
  • lecithine S6
  • lecithine is not necessary and is not added.
  • biocide (S7) there may be employed known products in the commercially available forms, e.g biocide based on l,2-benzoisotiazolin-3-one and l,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.
  • 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.
  • 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.
  • Component B can be obtained by heating the mentioned starting compounds at a temperature in the range 80 - 160 0 C, with water distillation if required, optionally under vacuum for 2 - 6 hours and in the presence of an organic solvent, if necessary.
  • ethoxylated products or ethoxylated and propoxylated products 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.
  • ethoxylation there is meant herein the addition reaction of ethylene oxide (also known as oxyethylation).
  • propoxylation there is meant herein the addition reaction of propylene oxide (also known as oxypropylation).
  • 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 0 C, preferably 130 to 220 0 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.
  • an alkali metal hydroxide e.g. sodium hydroxide or potassium hydroxide
  • 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.
  • the reaction of fatty acids with polyglycols can be carried out at a temperature in the range of 80-160 0 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.
  • Parts of component (B) are further reacted to synthesize (C) with sodium bisulphite at a temperature in the range of 60-120 0 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.
  • 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).
  • 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 0 C.
  • 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 0 C.
  • 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.
  • 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.
  • commercial retanning agents for example with vegetable tanning agents or synthetic organic tanning agents (syntans) based on phenolsulfonic acid/phenol/formaldehyde condensates
  • 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.
  • 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.
  • 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.
  • any hides, skins or pelts as conventionally processed in the beamhouse, tanned conventionally to get a wet blue or wet white leathers.
  • 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.
  • 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 -
  • Retanning and fatliquoring according to the invention may also be applied to leather intermediate products or non-finished leather (crusted leather).
  • 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.
  • retanning and fatliquoring bath there may e.g. be added one or more anionic surfactants (G) and/or a water miscible solvent (H).
  • G anionic surfactants
  • H water miscible solvent
  • surfactants (G) of anionic character there may be employed any conventional surfactants, preferably those containing a sulpho group, e.g. aliphatic or arylaliphatic sulphates (Gi) 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.
  • a sulpho group e.g. aliphatic or arylaliphatic sulphates (Gi) 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
  • Suitable sulphates (Gi) are e.g.:
  • G 1 ' 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
  • (Gi") sulphuric acid esters of fatty acid monoglycerides with e.g. 12 to 24 carbon atoms in the fatty acid radical
  • G 1 ' 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.
  • Suitable sulphonates (G 2 ) are e.g.
  • (G 1 ') there is meant the addition product of 1 to 10 moles of ethylene oxide to one mole of fatty alcohol.
  • (Gi) 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.
  • (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.
  • 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.
  • saturated aliphatic compounds of ether and/or alcohol character mainly mono-, di-, tri- and/or tetra-alkylene glycols and their mono- or di-(Ci_ 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 Methylene glycol, among which the monoalkylethers are preferred, especially diethylene glycol mono-butyl ether.
  • one or more anionic surfactants (G) and/or a water miscible solvent (H) can be added to the instant composition.
  • 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.
  • the temperature T of the retanning and fatliquoring bath advantageously is in the range of 20 to 60 0 C, preferably 30 to 60 0 C.
  • the pH may be as desidered and advantageously is in the range 3,0 - 6,5 .
  • 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.
  • 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.
  • At least a part of said composition may be combined with other retanning or fatliquoring products.
  • 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.
  • 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.
  • 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.
  • 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.
  • the bath is drained, again well washed with water from 50 to 400 % and drained again.
  • 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).
  • 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.
  • 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.
  • 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.
  • the substrate is drained, again well washed with water from 100 to 800 % and drained again.
  • 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).
  • the substrate may be directly further processed in the foreseen sequence of treatments for the production of the leather or pelt as 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.
  • 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.
  • the process of the invention there may be achieved an outstanding degree of retanning and fatliquoring of the substrate at once.
  • 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.
  • 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
  • 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 0 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 ).
  • reaction mass 323,8 g. of reaction mass is cooled down to 80-90 0 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 0 C and kept at 88 - 92 0 C for 30-40 minutes.
  • reaction mass is then heated up to 120 - 130 0 C and kept at 120 - 130 0 C for 2-3 hours, destilling water .
  • Amount of water to be destilled 6,3 g. of water.
  • 351,6 g of product prepared as indicated in example 1 are charged in reactor and heated to 80 - 90 0 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%.
  • the mixture is heated up to 85-98 0 C for 2-3 hours.
  • EXAMPLE 4 472 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.
  • 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.
  • 150 % of water and 2 % of sodium formate and 1 % of sodium bicarbonate are 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 0 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 0 C.
  • Other 0.5 % of formic acid is added and the drum is rotated for 20 minutes 40 0 C: pH is 3.6.
  • 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.
  • 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.
  • Wet Blue leathers half of a leather are given into a drum and 300 % of water at 40 0 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 0 C. The bath is drained. 300 % of water at 40 0 C is added and the goods are washed for 10 minutes, then the bath is drained.
  • a neutralising Syntan like Tanicor AS 6
  • the bath is drained. 200 % of water at 60 0 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 0 C. 0.5% of formic acid is added and the drum is rotated.
  • 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
  • the leather is retanned and fatliquored very regularly, is firm, tight, very soft and is optimally suitable for further processing in the tannery.
  • Wet Blue leather half of a leather are given into a drum and 200 % of water at 30 0 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 0 C, 5 % of Baychrom F (Chrom basic sulphate) are added and drumming is continued for 90 minutes at 35 - 40 0 C. The leather is left in the bath during the night.
  • a wetting agent like Tergolix W 01
  • Baychrom F Chrom basic sulphate
  • pH is 3.5. 100 % of water of 7°Be at 50 0 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°Be at 35 0 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 0 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. 50 % of water is added at 20 0 C, 1% of Dye (Bruno Melioderm G) is added and drum is rotated for 30 minutes. 100 % of water at 50 0 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.
  • Dye Bruno Melioderm G
  • the leather is retanned and fatliquored very regularly, is firm, tight, soft and are optimally suitable for further processing in the tannery.
  • Tannage Chrome % Based on: Shaved Weight

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Lubricants (AREA)
EP08865001.5A 2007-12-19 2008-12-09 Nachgerbmittel und fettlicker für leder Active EP2225399B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08865001.5A EP2225399B1 (de) 2007-12-19 2008-12-09 Nachgerbmittel und fettlicker für leder

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07024581 2007-12-19
PCT/EP2008/067062 WO2009080489A1 (en) 2007-12-19 2008-12-09 Retanning and fatliquoring agent for leather
EP08865001.5A EP2225399B1 (de) 2007-12-19 2008-12-09 Nachgerbmittel und fettlicker für leder

Publications (2)

Publication Number Publication Date
EP2225399A1 true EP2225399A1 (de) 2010-09-08
EP2225399B1 EP2225399B1 (de) 2013-11-20

Family

ID=39365833

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08865001.5A Active EP2225399B1 (de) 2007-12-19 2008-12-09 Nachgerbmittel und fettlicker für leder

Country Status (7)

Country Link
EP (1) EP2225399B1 (de)
KR (1) KR101603073B1 (de)
CN (1) CN101842499B (de)
AR (1) AR071273A1 (de)
BR (1) BRPI0819700B1 (de)
ES (1) ES2438276T3 (de)
WO (1) WO2009080489A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202200003698A1 (it) * 2022-02-28 2023-08-28 Stazione Sperimentale Per Lindustria Delle Pelli E Delle Materie Concianti S R L Procedimento di preparazione e di applicazione di olio vegetale conciante

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012128788A1 (en) 2011-03-24 2012-09-27 Elevance Renewable Sciences, Inc. Functionalized monomers and polymers
US9315748B2 (en) 2011-04-07 2016-04-19 Elevance Renewable Sciences, Inc. Cold flow additives
TWI576435B (zh) 2012-01-28 2017-04-01 斯塔國際公司 加脂劑與加脂方法
US9012385B2 (en) 2012-02-29 2015-04-21 Elevance Renewable Sciences, Inc. Terpene derived compounds
CN102586510B (zh) * 2012-03-21 2013-07-31 陕西科技大学 含有改性氧化石墨烯皮革加脂剂的制备方法
CN103667546A (zh) * 2012-09-24 2014-03-26 天津博克尼科技发展有限公司 一种复合型皮革加脂剂
US20150057204A1 (en) 2013-03-12 2015-02-26 Elevance Renewable Sciences, Inc. Maleanized Ester Derivatives
US20140274832A1 (en) 2013-03-12 2014-09-18 Elevance Renewable Sciences, Inc. Maleinized ester derivatives
EP3094755B1 (de) * 2014-01-16 2023-04-26 Corichem S.r.l. Polymere fettungsmittel
CN103833613B (zh) * 2014-02-08 2016-01-13 上海金兆节能科技有限公司 脂肪酸聚氧乙烯琥珀酸酯磺酸盐及其制备方法和用途
CN106755633A (zh) * 2016-11-15 2017-05-31 王鲁燕 一种新型两亲共聚物复鞣加脂剂及制备方法
CN106399600A (zh) * 2016-11-15 2017-02-15 王鲁燕 一种新型合成加脂剂及制备方法
NL2033083B1 (en) 2022-09-20 2024-03-26 Stahl Int B V Grafted polymer of mono-unsaturated polycarboxylic acid as dyeing auxiliary or as re-tanning agent for leather

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5279613A (en) * 1989-08-08 1994-01-18 Basf Aktiengesellschaft Copolymers based on long-chain olefins and ethylenically unsaturated dicarboxylic anhydrides for rendering leathers and skins water-repellent
DE4026235A1 (de) * 1990-08-18 1992-02-20 Wella Ag Persulfathaltige zubereitung in form eines granulats, 2-komponenten-mittel und verfahren zum entfaerben und blondieren von haaren
DE4236556A1 (de) * 1992-10-29 1994-05-05 Stockhausen Chem Fab Gmbh Verfahren zur Weichmachung/Fettung von Ledern und Pelzen
DE4240159A1 (de) * 1992-11-30 1994-06-01 Henkel Kgaa Sulfitierte Fettstoffe mit vermindertem Gehalt an freiem Hydrogensulfit
DE4402029A1 (de) * 1994-01-25 1995-07-27 Basf Ag Wäßrige Lösungen oder Dispersionen von Copolymerisaten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009080489A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202200003698A1 (it) * 2022-02-28 2023-08-28 Stazione Sperimentale Per Lindustria Delle Pelli E Delle Materie Concianti S R L Procedimento di preparazione e di applicazione di olio vegetale conciante

Also Published As

Publication number Publication date
BRPI0819700B1 (pt) 2019-03-26
CN101842499A (zh) 2010-09-22
EP2225399B1 (de) 2013-11-20
ES2438276T3 (es) 2014-01-16
KR101603073B1 (ko) 2016-03-14
KR20100112554A (ko) 2010-10-19
CN101842499B (zh) 2014-12-03
WO2009080489A1 (en) 2009-07-02
BRPI0819700A2 (pt) 2015-06-16
AR071273A1 (es) 2010-06-09

Similar Documents

Publication Publication Date Title
EP2225399B1 (de) Nachgerbmittel und fettlicker für leder
KR101849065B1 (ko) 비-금속 태닝 방법
KR101849518B1 (ko) 비금속 태닝
KR101845691B1 (ko) 비금속 태닝
KR101849517B1 (ko) 비금속 태닝
KR101849519B1 (ko) 비금속 태닝
TWI576435B (zh) 加脂劑與加脂方法
WO2013023979A1 (de) Verfahren zum färben von collagenfaserhaltigen substraten
EP1831405B1 (de) Zusammensetzung zur behandlung von leder
US20100154128A1 (en) Method for producing leather
US5492539A (en) Method of preparing leather from unhaired hides
AU718011B2 (en) Aqueous polymer dispersion, process for preparing the same and its use in leather production
US20070294835A1 (en) Process and Compositions for Wet Degreasing of Pelts, Skins, Hides, Leather Intermediate Products and Non-Finished Leather
CN109576417B (zh) 一种氨基复鞣加脂剂及其制备方法
TW201326401A (zh) 用於染色膠原纖維基材之方法
US20060143833A1 (en) Leather degreasing agent
US20030092807A1 (en) Leather waterproofing formulation and leather goods waterproofed therewith
NL2033083B1 (en) Grafted polymer of mono-unsaturated polycarboxylic acid as dyeing auxiliary or as re-tanning agent for leather
US20060096036A1 (en) Method for hydrophobing leather and furskins
KR20050097973A (ko) 피혁 제조 방법
US5527360A (en) Fatliquoring, filling and hydrophobicizing leathers and furs
US20070192962A1 (en) Aqueous Compositions Containing Alkoxylated Alcohols And Hydrophobic Components, Method For The Production And Use Thereof
EP1805328B1 (de) Verfahren zur herstellung von leder und dafür geeignete verbindungen
US8642185B2 (en) Leather production and aqueous formulations suitable therefor
DE10251141A1 (de) Verfahren zur Herstellung von Leder und Pelzfellen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20100719

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

RIN1 Information on inventor provided before grant (corrected)

Inventor name: GAMARINO, ROBERTA

Inventor name: GIANI, MICHELE

Inventor name: REINEKING, CLAUS

Inventor name: TRIMARCO, LICIA

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20130514

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20130807

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

RBV Designated contracting states (corrected)

Designated state(s): AT CH DE ES FR GB IT LI NL TR

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT CH DE ES FR GB IT LI NL TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 641710

Country of ref document: AT

Kind code of ref document: T

Effective date: 20131215

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2438276

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20140116

Ref country code: DE

Ref legal event code: R096

Ref document number: 602008028927

Country of ref document: DE

Effective date: 20140116

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20131206

Year of fee payment: 6

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: CLARIANT INTERNATIONAL LTD., CH

Free format text: FORMER OWNER: CLARIANT FINANCE (BVI) LIMITED, VG

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602008028927

Country of ref document: DE

Representative=s name: MIKULECKY, KLAUS, DIPL.-CHEM. DR.PHIL.NAT., DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: SD

Effective date: 20140418

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602008028927

Country of ref document: DE

Representative=s name: VEREENIGDE OCTROOIBUREAUX V.O., DE

Effective date: 20140408

Ref country code: DE

Ref legal event code: R082

Ref document number: 602008028927

Country of ref document: DE

Representative=s name: MIKULECKY, KLAUS, DIPL.-CHEM. DR.PHIL.NAT., DE

Effective date: 20140408

Ref country code: DE

Ref legal event code: R081

Ref document number: 602008028927

Country of ref document: DE

Owner name: CLARIANT INTERNATIONAL LTD., CH

Free format text: FORMER OWNER: CLARIANT FINANCE (BVI) LTD., ROAD TOWN, VG

Effective date: 20140408

Ref country code: DE

Ref legal event code: R081

Ref document number: 602008028927

Country of ref document: DE

Owner name: STAHL INTERNATIONAL BV, NL

Free format text: FORMER OWNER: CLARIANT FINANCE (BVI) LTD., ROAD TOWN, TORTOLA, VG

Effective date: 20140408

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20140424 AND 20140430

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602008028927

Country of ref document: DE

Representative=s name: VEREENIGDE OCTROOIBUREAUX V.O., DE

Ref country code: DE

Ref legal event code: R082

Ref document number: 602008028927

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Owner name: CLARIANT INTERNATIONAL LTD, CH

Effective date: 20140519

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008028927

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: STAHL INTERNATIONAL B.V., NL

Free format text: FORMER OWNER: CLARIANT INTERNATIONAL LTD., CH

Ref country code: CH

Ref legal event code: NV

Representative=s name: PATENTANWAELTE SCHAAD, BALASS, MENZL AND PARTN, CH

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20140918 AND 20140924

26N No opposition filed

Effective date: 20140821

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602008028927

Country of ref document: DE

Owner name: STAHL INTERNATIONAL BV, NL

Free format text: FORMER OWNER: CLARIANT INTERNATIONAL LTD., MUTTENZ, CH

Effective date: 20140918

Ref country code: DE

Ref legal event code: R082

Ref document number: 602008028927

Country of ref document: DE

Representative=s name: VEREENIGDE OCTROOIBUREAUX V.O., DE

Effective date: 20140523

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: CLARIANT INTERNATIONAL LTD.

Effective date: 20141107

Ref country code: FR

Ref legal event code: TP

Owner name: STAHL INTERNATIONAL BV, NL

Effective date: 20141013

REG Reference to a national code

Ref country code: NL

Ref legal event code: SD

Effective date: 20141120

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008028927

Country of ref document: DE

Effective date: 20140821

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: STAHL INTERNATIONAL BV

Effective date: 20141201

REG Reference to a national code

Ref country code: AT

Ref legal event code: PC

Ref document number: 641710

Country of ref document: AT

Kind code of ref document: T

Owner name: STAHL INTERNATIONAL B.V., NL

Effective date: 20150505

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141231

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230508

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20231121

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231220

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20231207

Year of fee payment: 16

Ref country code: IT

Payment date: 20231228

Year of fee payment: 16

Ref country code: FR

Payment date: 20231221

Year of fee payment: 16

Ref country code: DE

Payment date: 20231214

Year of fee payment: 16

Ref country code: AT

Payment date: 20231221

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20240126

Year of fee payment: 16