EP0792377A1 - Procede de preparation de cuir et de fourrures au moyen de matieres tannantes polymeres - Google Patents

Procede de preparation de cuir et de fourrures au moyen de matieres tannantes polymeres

Info

Publication number
EP0792377A1
EP0792377A1 EP95937048A EP95937048A EP0792377A1 EP 0792377 A1 EP0792377 A1 EP 0792377A1 EP 95937048 A EP95937048 A EP 95937048A EP 95937048 A EP95937048 A EP 95937048A EP 0792377 A1 EP0792377 A1 EP 0792377A1
Authority
EP
European Patent Office
Prior art keywords
tanning
polymer
weight
acrylic
group
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.)
Withdrawn
Application number
EP95937048A
Other languages
German (de)
English (en)
Inventor
Manfred Breth
Jürgen CARLE
Hermann Birkhofer
Michael Kneip
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP0792377A1 publication Critical patent/EP0792377A1/fr
Withdrawn legal-status Critical Current

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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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes
    • 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
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/22—Chemical tanning by organic agents using polymerisation products
    • 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 present invention relates to an improved process for the production of leather and fur skins using polymer tanning agents.
  • the tannery wastewater has to be freed of chromium salts, shavings and cut leather remnants have to be disposed of in hazardous waste landfills.
  • the process according to the invention is usually carried out by pretanning using aldehydes or reactive carbonyl compounds, polymer tanning agents or a mixture thereof, and tanning using one or more polymer tanning agents or a mixture of polymer tanning agents and fatliquoring agents.
  • the subsequent tanning process represents the actual tanning step.
  • polymer tanning agents often have more or less greasy properties at the same time, which in some cases can be made the dominant property by modification in the tanning agent formulation, for example by adding emulsifiers. In principle, however, all customary non-tanning fatliquoring agents can also be used in the process of tanning.
  • ketocarboxylic acids with 3 to 10 carbon atoms or
  • aliphatic dialdehydes there are in particular saturated structures, i.e. Structures without other reactive centers, such as double bonds or triple bonds, are suitable.
  • the aliphatic chain can be interrupted by one or more non-adjacent oxygen atoms.
  • ⁇ , ⁇ -dialdehydes such as glyoxal, malondialdehyde, succindialdehyde, glutardialdehyde, 3-oxaglutardialdehyde, adipindialdehyde, pimeline dialdehyde and the dialdehyde derived from suberic acid are suitable.
  • Aromatic dialdehydes (b) include, for example, terephthalaldehyde, naphthalene dialdehydes or 2,5-dimethyl terephthalaldehyde.
  • Araliphatic dialdehydes (c) include, for example p-phenylene-diacetaldehyde, p-phenylene-di-3-propionaldehyde and p-phenylene-di-4-butyraldehyde. Compounds with an aromatic and an aliphatic aldehyde function should also be mentioned here, e.g. p-formylphenylacetaldehyde.
  • aldehyde carboxylic acids (d) ⁇ -aldehyde carboxylic acids such as malonic acid monoaldehyde, succinic acid monoaldehyde, glutaric acid monoaldehyde, adipic acid monoaldehyde, pimelic acid monoaldehyde or kor acid monoaldehyde are particularly suitable.
  • Glyoxylic acid is of particular interest here.
  • ketocarboxylic acids (e) are pyruvic acid, levulinic acid, mesoxalic acid, ⁇ -oxoglutaric acid and oxaloacetic acid.
  • ⁇ -ketocarboxylic acids are preferred.
  • dialdehydes (a) to (c) are in the form of acetals, both aldehyde functions are usually acetalized. However, compounds with only one acetalized aldehyde function can be used in the process according to the invention.
  • alkali to C 3 -alkanols such as methanol, ethanol, n-propanol or isopropanol and alkanediols, which are cyclic with the aldehyde function, can be used as the alcohols
  • Form acetal for example 1,2-ethylene glycol or 1,3-propylene glycol, can be used.
  • those used for acetalization used alcohols with 1 to 50 mol, in particular 2 to 30 mol, especially 3 to 15 mol ethylene oxide or propylene oxide or a mixture thereof per hydroxyl group, examples of which are correspondingly ethoxylated or propoxylated methanol, ethanol, n-propanol, n-butanol, ethylene glycol or propylene glycols.
  • Formaldehyde (f) is just as good as the compounds (a) to (e) with regard to the stabilizing effect on the nakedness, but is often avoided for ecological reasons.
  • aliphatic dialdehydes (a) having 2 to 5 carbon atoms are particularly preferred, in particular glyoxal, glutardialdehyde and 3-oxaglutaraldehyde.
  • Suitable polymeric tanning agents for the pretanning step as well as for the tanning step of the process according to the invention are suitably effective homo-, co-, ter- or graft polymers.
  • these are polymers containing carboxyl groups.
  • the following groups of substances are particularly suitable:
  • C) copolymers and terpolymers of C 2 - to C -01efinen (CD with acrylic or methacrylic acid (C2) or with acrylic or methacrylic acid-Ci to C 3 o-alkyl or -C 2 - to C 3 o-alkenyl esters, preferably Ci to C 2 o-al yl (meth) acrylates, (C3) or with a mixture of (C2) and (C3) in a weight ratio of 95: 5 to 5:95, in particular 95 : 5 to 70:30, for copolymers or of (CD: [(C2) + C3)] 95: 5 to 5:95, in particular 95: 5 to 70:30 for terpolymers, where (C2) and ( C3) can be in a weight ratio of 99.5: 0.5 to 0.5: 99.5, a molecular weight of 2,000 to 100,000, for example acrylic or methacrylic acid / ethylene copolymers, acrylic or methacrylic acid / propylene copo
  • Copolymers obtained by radical copolymerization of C ⁇ to C o monoolefins with ethylenically unsaturated C to C ⁇ dicarboxylic acid anhydrides, e.g. Maleic anhydride (MA), obtainable in the manner of bulk polymerization at temperatures from 80 to 300 ° C. to copolymers with molar masses from 500 to 20,000, subsequent solvolysis of the anhydride groups of the copolymers and at least partial neutralization of the carboxyl groups formed during solvolysis in an aqueous medium with bases are; such polymers are described for example in DE-A 39 26 167;
  • MA Maleic anhydride
  • Copolymers which are obtained by radical copolymerization of C ⁇ - to C o-alkyl vinyl ethers or hybrids of ⁇ - to C o-alkyl vinyl ethers and up to 50 mol% of C ⁇ - to C o-mono-olefins with ethylenically unsaturated C - to C ⁇ - Dicarboxylic acid anhydrides, e.g.
  • Maleic anhydride (MA) for copolymers with molecular weights of 500 to 20,000, subsequent solvolysis of the anhydride groups of the copolymers and at least partial neutralization of the carboxyl groups formed during solvolysis are obtainable in an aqueous medium with bases; such polymers are described for example in DE-A 39 26 168;
  • C ⁇ to C o-alkyl acrylates 50 to 90% by weight of C ⁇ to C o-alkyl acrylates, C ⁇ to C o alkyl methacrylates, vinyl esters of C ⁇ to C 4 o-carboxylic acids or mixtures thereof and 10 to 50% by weight of monoethylenically unsaturated C 3 to C 12 carboxylic acids, monoethylenically unsaturated dicarboxylic acid anhydrides, half esters or half amides of monoethylenically unsaturated C to C 2 dicarboxylic acids, A ide of monoethylenically unsaturated C 3 to C 1 2 -monocarboxylic acids or mixtures thereof
  • polymers contain polymerized and have a molecular weight of 500 to 30,000, in at least partially neutralized form; such polymers are described for example in DE-A 39 31 039:
  • R 1 , R 2 and R 3 are hydrogen, methyl or ethyl and k is 1 or 2
  • Such graft polymers are described, for example, in DE-A 42 02 452;
  • X (CH 2 ) r 'r _> 2 and Y represents a carboxyl group or an OCOR 7 radical, a COOR 8 radical or a CONR 9 R 10 radical and Z represents hydrogen or a lower one is alkyl, wherein R 7 is a C ⁇ -C 2 _ o alkyl radical, wherein R 8 is a C ⁇ -C 3 -alkyl radical or an alkoxylation product thereof, wherein R 9 and R 10 is hydrogen or an alkyl radical (C 1 to C 20) represent and may be different;
  • Such copolymers preferably have a molecular weight of 800 to 30,000;
  • typical examples of the first component are maleic anhydride and dibutyl maleate
  • typical examples of the second component are an undecenoic acid derivative or a
  • R 12 HC - C (Rn) - COOH III where Rn is hydrogen, methyl or a group -CH 2 COOH
  • R 12 represents hydrogen, methyl, phenyl or a group
  • Carboxyl groups are in the molecule, or on monomers of the formula III-A
  • Ri 3 for hydrogen or methyl and R ⁇ for an alkyl radical or cycloalkyl radical with 1 to 12 carbon atoms substituted with at least one hydroxyl group
  • R ⁇ 5 is an alkyl radical having 1 to 2 carbon atoms
  • VI CH 2 C COORie in which R 1 3 represents hydrogen or methyl and Ri 6 represents an optionally cyclic alkyl radical having 1 to 12 carbon atoms;
  • R ⁇ 7 is hydrogen or the methyl radical, Ri ⁇ and R 19 , which are the same or different, denote the methyl or ethyl radical, T for an optionally branched Alkylene radical having 1 to 5 carbon atoms and the amine nitrogen is optionally neutralized or quaternized, with a molecular weight of the copolymers, measured at a pH of 8.0, of less than 100,000;
  • R 21 COOR 23 , CH 2 OR 23 , CH 2 N (R 23 ) 2
  • R 24 H or -CC -alkyl
  • R 27 H, -CC 24 alkyl, C 6 -C 2 aryl, C 7 -C 24 alkylaryl,
  • non-tanning fatliquors especially those from the following groups of substances can be used: 10 natural fatliquors of animal origin, e.g. Fish oil, whale oil, cattle claw oil or tallow;
  • natural fatliquors of plant origin e.g. 15 cottonseed oil, castor oil, sunflower oil, peanut oil or olive oil;
  • Hydrocarbons e.g. Paraffin oil, low molecular weight mineral oil and low molecular weight polyethylene or polypropylene as aqueous dispersions;
  • paraffin derivatives such as chlorinated or sulfochlorinated paraffins
  • Polyalkylene oxides such as polyethylene oxide, polypropylene oxide or ethylene oxide-propylene oxide block copolymers as aqueous dispersions.
  • non-tanning fatliquors are mostly pre-emulsified in 30 aqueous systems and usually contain emulsifiers.
  • emulsifiers such as emulsions or dispersions can furthermore contain organic solvents in order to promote deeper penetration and uniform distribution over the entire leather surface.
  • the polymer tanning agents mentioned are usually in the form of aqueous solutions or aqueous dispersions in amounts of 3 to 100% by weight, preferably 10 to 50% by weight, of solid, based on the shaved weight, in the tanning step and in amounts of 0 to 40 50% by weight .-%, preferably 0 to 30 wt .-% solids, based on the pelt weight, used in the pretanning steps.
  • non-tanning fatliquors are also used in the tanning step, they can be used in amounts of up to 80% by weight, preferably 45% up to 40% by weight, of solid, based on the fold weight.
  • the weight ratio of polymer tanning agents to Non-tanning fatliquoring agents are in particular 99: 1 to 20:80, especially 95: 5 to 35:65.
  • the aldehydes or reactive carboxyl compounds mentioned in the pretanning step are normally used in amounts of 0.1 to 15% by weight, preferably 1 to 7% by weight, based on the weight of the raw material. If a mixture of polymer tanning agents and aldehydes or reactive carbonyl compounds is used here, the amount of aldehydes or reactive carbonyl compounds is usually reduced depending on the proportion of polymer tanning agents in the mixture.
  • the weight ratio of polymer tanning agents to aldehydes or reactive carbonyl compounds is in particular 99: 1 to 1:99, especially 90:10 to 10:90.
  • the following are used as polymer tanning agents or a mixture of polymer tanning agents and fatliquoring agents in the tanning step:
  • Anhydrides or their salts in a weight ratio of 99: 1 to 10:90, in particular 90:10 to 30:70;
  • the aldehydes or reactive carbonyl compounds used in the pretanning step are the abovementioned preferred aldehydes, alone or in a mixture with acrylic or methacrylic acid homopolymers (according to group A). Furthermore, in another particularly preferred embodiment, acrylic or methacrylic acid homopolymers (according to group A) are used alone in the pretanning step without aldehydes or reactive carbonyl compounds.
  • the leather and fur skins tanned by the process according to the invention can be aftertreated and finished, as usual, in a colored manner.
  • the pretreatment of the bare skin before tanning, i.e. switch, liming, liming and pimples in particular are carried out as usual in the tannery.
  • the leather and fur skins produced by the process according to the invention have high qualities with regard to their physical fastness, in particular light fastness and heat yellowing stability.
  • the leathers are usually very soft, and the degree of softness can be controlled by the amount and type of polymer tanning agents.
  • the method according to the invention is universally applicable because it is suitable for the production of all types of leather of the most varied provenance.
  • the method according to the invention is extremely advantageous both economically and ecologically. It can be carried out easily and without problems and is inexpensive since the polymer tanning agents and aldehydes or reactive carbonyl compounds used are generally not expensive special chemicals. By avoiding the otherwise common environmentally harmful vegetable, synthetic and mineral tannins, the process according to the invention becomes extremely attractive. The wastewater pollution due to the better wasting of the tanning liquors is at significantly lower values. Examples
  • South German beef skin was soaked, cremated and descaled as usual and washed with 200% water at 25 ° C for 10 min. After the liquor had been drained, 40% of water at 25 ° C. and 6% of sodium chloride were added, after 10 minutes of 2% of 17% by weight aqueous formic acid and after a further 30 minutes of 8% of 10% by weight sulfuric acid ; the pH was then 3.0.
  • the tanning took place after addition of a further 100% of water at 30 ° C. by the action of 6% of a 33% by weight aqueous dispersion or solution of the agent I for 60 minutes and then three times in each case 30% of a 33% by weight .-% aqueous dispersion or solution of a mixture of equal parts by weight of agent I and agent II for 90 minutes each for the first and second addition and overnight for the third addition.
  • the pH was then 4.9.
  • the leathers obtained according to Examples 4 to 10 were all satisfactory to very good in their properties, in particular they performed extremely well in the assessment of the light fastness and the heat yellowing stability.
  • the leather from Example 10 was given a rating of 4 in the Xeno-Test ® exposure (according to IUF 402) and a rating of 4 in the heat yellowing test (4 hours at 110 ° C.), whereas corresponding synthetic or vegetable tanned leather in these two tests only received grade 2 in each case.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

L'invention concerne un procédé de production de cuir et de fourrures par tannage sans matières tannantes végétales, synthétiques et minérales, mais uniquement avec des matières tannantes polymères. Le cas échéant, des aldéhydes ou des composés de carbonyle réactifs peuvent être utilisés lors du prétannage.
EP95937048A 1994-11-15 1995-11-03 Procede de preparation de cuir et de fourrures au moyen de matieres tannantes polymeres Withdrawn EP0792377A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4440846 1994-11-15
DE19944440846 DE4440846A1 (de) 1994-11-15 1994-11-15 Verfahren zur Herstellung von Leder und Pelzfellen unter Verwendung von Polymergerbstoffen
PCT/EP1995/004318 WO1996015276A1 (fr) 1994-11-15 1995-11-03 Procede de preparation de cuir et de fourrures au moyen de matieres tannantes polymeres

Publications (1)

Publication Number Publication Date
EP0792377A1 true EP0792377A1 (fr) 1997-09-03

Family

ID=6533417

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95937048A Withdrawn EP0792377A1 (fr) 1994-11-15 1995-11-03 Procede de preparation de cuir et de fourrures au moyen de matieres tannantes polymeres

Country Status (5)

Country Link
EP (1) EP0792377A1 (fr)
JP (1) JPH10508644A (fr)
AU (1) AU3927395A (fr)
DE (1) DE4440846A1 (fr)
WO (1) WO1996015276A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006000592A1 (fr) 2004-06-28 2006-01-05 Basf Aktiengesellschaft Utilisation de polymeres contenant des groupes ether en tant qu'agents de solubilisation

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003232247A1 (en) 2002-05-07 2003-11-11 Basf Aktiengesellschaft Tanning agent and curing agent based on dialdehydes
US7270985B2 (en) * 2003-09-15 2007-09-18 Council Of Scientific & Industrial Research Process for the preparation of aldehyde from a proteinous source for industrial applications
JP4689178B2 (ja) * 2004-03-05 2011-05-25 協伸株式会社 インクジェットにより染色した皮革の製造方法および該方法により染色した皮革
DE102005012329A1 (de) 2005-03-17 2006-09-28 Lanxess Deutschland Gmbh Verfahren zur Hydrophobierung von Leder mittels Alkylalkoxysilanen sowie hydrophobiertes Leder
JP5172228B2 (ja) * 2007-06-28 2013-03-27 ミドリホクヨー株式会社 革
RU2494151C2 (ru) * 2008-05-16 2013-09-27 Мидори Хокуйо Ко., Лтд. Верхнее покрытие
JP2010144061A (ja) * 2008-12-19 2010-07-01 Midori Hokuyo Kk 革
KR101875237B1 (ko) 2010-05-28 2018-07-05 모멘티브 퍼포먼스 머티리얼즈 게엠베하 섬유상 물질의 폴리오르가노실록산으로의 소수성화

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1176788B1 (de) * 1960-06-02 1964-08-27 Cassella Farbwerke Mainkur Ag Gerben von Pelzfellen
US3408319A (en) * 1964-12-08 1968-10-29 Rohm & Haas Tanning compositions comprising aqueous solutions of unsaturated acid-unsaturated sulfated oil copolymers
US4526581A (en) * 1983-02-07 1985-07-02 Rohm And Haas Company Process for producing leather
US5348807A (en) * 1991-02-05 1994-09-20 Rohm And Haas Company Polymeric retan fatliquor for low fogging upholstery leather
DE4242076A1 (de) * 1992-12-14 1994-06-16 Roehm Gmbh Gerbmittel und Gerbverfahren

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9615276A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006000592A1 (fr) 2004-06-28 2006-01-05 Basf Aktiengesellschaft Utilisation de polymeres contenant des groupes ether en tant qu'agents de solubilisation

Also Published As

Publication number Publication date
AU3927395A (en) 1996-06-06
JPH10508644A (ja) 1998-08-25
DE4440846A1 (de) 1996-05-23
WO1996015276A1 (fr) 1996-05-23

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