EP0607388A1 - Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils. - Google Patents

Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils.

Info

Publication number
EP0607388A1
EP0607388A1 EP93915893A EP93915893A EP0607388A1 EP 0607388 A1 EP0607388 A1 EP 0607388A1 EP 93915893 A EP93915893 A EP 93915893A EP 93915893 A EP93915893 A EP 93915893A EP 0607388 A1 EP0607388 A1 EP 0607388A1
Authority
EP
European Patent Office
Prior art keywords
monomers
weight
acid
monoethylenically unsaturated
use according
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
EP93915893A
Other languages
German (de)
English (en)
Other versions
EP0607388B1 (fr
Inventor
Hermann Birkhofer
Peter Danisch
Walter Denzinger
Heinrich Hartmann
Michael Kneip
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BASF SE
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BASF SE
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Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes

Definitions

  • the greasing is a quality-determining process in the production of leather and especially important in the case of very soft types of leather.
  • aqueous fat emulsions (licker) are used, which are generally based on petrochemical products and natural oils and fats and made water-soluble by partial sulfation or with the help of emulsifiers.
  • Patent application P 42 05 839.2 describes polymeric leather greasing agents based on esterified or modified homo- or copolymers of monoethylenically unsaturated dicarboxylic acid anhydrides, which, depending on the degree of derivatization of the carboxyl groups and the "polarity of the monomers in hydrophobicized leather, to a certain extent The water-repellent properties of the leather can deteriorate, and this application also describes further prior art.
  • the invention was based on the object of providing improved means for greasing and filling leather and fur skins which no longer have the disadvantages of the prior art.
  • the object is achieved according to the invention by using water-soluble or water-dispersible graft copolymers of vegetable and animal oils, obtainable by free-radically initiated polymerization according to claim 1.
  • Mono ere (a) are e.g. monoethylenically unsaturated mono- and dicarboxylic acids with preferably 3 to 12 carbon atoms in the molecule, such as acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, allylacetic acid, vinyl acetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or methylene malonic acid and the corresponding anhy- acid dride.
  • monoethylenically unsaturated mono- and dicarboxylic acids with preferably 3 to 12 carbon atoms in the molecule, such as acrylic acid, methacrylic acid, dimethylacrylic acid, ethyl acrylic acid, allylacetic acid, vinyl acetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or methylene malonic acid and the corresponding anhy- acid dride.
  • Examples of monomers containing sulfo groups include Vinyl sulfonic acid, allylsulfonic acid, methallylsulfonic acid, acrylic acid 3-sulfopropyl ester, methacrylic acid 3-sulfopropyl ester, styrene sulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid.
  • Monomers with phosphonic acid groups are, for example, vinylphosphonic acid, allylphosphonic acid, phosphonomethylated allylamine and acrylamido-2-methylpropanephosphonic acid.
  • Preferred monomers of group (a) are acrylic acid, methacrylic acid and maleic acid. It can also be advantageous to use mongrels of monomers (a).
  • the acids are preferably used as such or as anhydrides; in addition, alkali metal, alkaline earth metal or ammonium salts, such as the sodium, potassium, calcium, ammonium or substituted ammonium salts, can of course also be used, the All or part of the acids can be present as salts.
  • Monomers (b) which can be copolymerized with the monomers (a) include, in particular, N-vinylpyrrolidone, N-vinylcaprolacta, N-vinylimidazole, l-vinyl-2-methylimidazole, N-vinylformamide, N- Vinyl-N-methylformamide, vinyl acetate, vinyl propionate, styrene, acrylic acid and methacrylic acid esters with Ci- to C 3 o-alcohols, hydroxy-C 2 - to C ⁇ -alkyl esters of acrylic acid or methacrylic acid, acrylamide, methacrylamide or mono- and dialkylamides of acrylic acid and methacrylic acid with 1 to 20 carbon atoms in the alkyl radicals.
  • olefins having 2 to 30 carbon atoms and vinyl alkyl ethers are also used as monomers (b) with 1 to 30 carbon atoms in the alkyl radical are particularly suitable.
  • olefins having 2 to 30 carbon atoms and vinyl alkyl ethers are also used as monomers (b) with 1 to 30 carbon atoms in the alkyl radical are particularly suitable.
  • a further modification of the graft copolymers can be achieved by carrying out the graft polymerization in the presence of monomers from group (c).
  • the monomer mixtures contain up to 5% by weight of a monomer having at least two ethylenically unsaturated non-conjugated double bonds in the molecule.
  • These compounds are usually used as crosslinkers in copolymerizations. They can be added to the monomers of group (a) used for the copolymerization or to the monomer mixtures from (a) and (b). If they are used, the preferred amount of monomers (c) is 0.05 to 2% by weight.
  • the use of the monomers of group (c) during the copolymerization increases the K values of the copolymers.
  • Suitable compounds of this type are, for example, methylene bisacrylic acid, esters of acrylic acid and methacrylic acid with polyhydric alcohols, e.g. Glycol diacrylate, glycerol triacrylate, glycol dimethacrylate, glycerol trimethacrylate, and at least two polyols esterified with acrylic acid or methacrylic acid, such as pentaerythritol and glucose.
  • Suitable crosslinkers are also divinylbenzene, divinyldioxane, pentaerythritol triallyl ether and pentaallylsucrose. From this group of compounds, water-soluble monomers, such as glycol diacrylate or glycol diacrylates of polyethylene glycols with a molecular weight of up to 3,000, are preferably used.
  • component B includes all vegetable and animal oils. There are, for example, olive oil, rapeseed oil, soybean oil, sunflower oil, safflower oil, linseed oil, capelan oil or sperm oil.
  • the monomers (a) and optionally (b) and / or (c) are polymerized by free radicals in the presence of component B. It may be favorable for the effect of the graft polymer formed to use two or more of the oils specified under B.
  • the polymerization can be carried out in the presence or in the absence of inert solvents or diluents, with the absence of diluents being preferred.
  • Inert solvents are, for example, aromatic hydrocarbons such as toluene, xylene, o-, -, p-xylene and isomer mixtures of xylene or ethylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, dodecane, cyclohexane, Cyclooctane, methylcyclohexane or mixtures of the hydrocarbons mentioned and gasoline fractions which contain no polymerizable monomers.
  • aromatic hydrocarbons such as toluene, xylene, o-, -, p-xylene and isomer mixtures of xylene or ethylbenzene
  • aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, dodecane, cyclohexane,
  • chlorinated hydrocarbons such as chloroform, carbon tetrachloride, hexachloroethane, dichloroethane or tetrachloroethane, alcohols such as methanol, ethanol, isopropanol, n-propanol, n-butanol or sec-butanol as well as tetrahydrofuran, dioxane and mixtures of the named inert are suitable Solvents.
  • the graft polymerization can be carried out continuously or batchwise, in general initiators which form free radicals are also used.
  • Suitable radical-forming initiators are preferably those which have a half-life of less than 3 hours at the polymerization temperature chosen in each case. If the polymerization is initially started at a lower temperature and ends at a higher temperature, it is advisable to work with at least two initiators which disintegrate at different temperatures, namely firstly using an initiator which already disintegrates at a lower temperature for the start of the polymerization and then complete the main polymerization with an initiator that decomposes at a higher temperature. For example, the following initiators can be used.
  • Acetylcyclohexanesulfonyl peroxide diacetyl peroxidicarbonate, dicyclohexyl peroxidicarbonate, di-2-ethylhexyl peroxidicarbonate, tert-butyl perneodecanoate, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis- (2- methyl- N-phenylpropionamidine) dihydrochloride, 2,2'-azobis- (2-methylpropionamidine) dihydrochloride.
  • a redox system such as salts or complexes of heavy metals, for example copper, cobalt, manganese, iron, vanadium, cerium, nickel and chromium salts or organic compounds such as benzoin, dimethylaniline or ascorbic acid are used , the half-lives of the radical initiators indicated can be reduced.
  • tert-butylhydroperoxide can be activated with the addition of 5 ppm copper (II) acetylacetonate in such a way that polymerisation can take place at 100 ° C.
  • the reducing component of redox catalysts can also be formed, for example, from compounds such as sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. Based on the monomers used in the polymerization, 0.01 to 20, preferably 0.05 to 10,% by weight of a polymerization initiator or a mixture of several polymerization initiators is used. 0.01 to 5% of the reducing compounds are added as redox components. Heavy metals are used in the range of 0.1 to 100 ppm, preferably 0.5 to 10 ppm. It is often beneficial to use a combination of peroxide, and Use reducing agent and heavy metal as a redox catalyst.
  • the polymerization of the monomers (a) and the optionally used monomers (b) and / or (c) can also be carried out by the action of ultraviolet radiation, if appropriate in the presence of UV initiators.
  • the photoinitiators or sensitizers that are normally used are used. These are, for example, compounds such as benzoin and benzoin ether, ⁇ -methylbenzoin or ⁇ -phenylbenzoin. So-called triplet sensitizers, such as benzene diketals, can also be used.
  • high-energy UV lamps such as carbon arc lamps, mercury vapor lamps or xenon lamps
  • low-UV light sources such as fluorescent tubes with a high proportion of blue, also serve as UV radiation sources.
  • Suitable regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan.
  • Allyl compounds such as allyl alcohol, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydrazine sulfate and butenols are also suitable as regulators. If the polymerization is carried out in the presence of regulators, from 0.05 to 20% by weight, based on the monomers used in the polymerization, is required.
  • the polymerization is carried out in the presence of water-soluble phosphorus compounds in which the phosphorus has an oxidation number of 1 to 4, the water-soluble alkali metal or ammonium salts thereof zen, water-soluble -PO (OH) "groups containing compounds and / or their water-soluble salts.
  • Phosphorous acid is preferably used.
  • the phosphorus compounds in question are used to reduce the discoloration of the graft copolymers in amounts of 0.01 to 5% by weight. %, based on the monomers (A) used Possible phosphorus compounds are described in EP-A-0 175 317.
  • the copolymerization of components (A) and (B) is usually carried out in an inert gas atmosphere with the exclusion of atmospheric oxygen. Good mixing of the reactants is generally ensured during the polymerization.
  • the reactants which are preferably present in an inert diluent, can be copolymerized discontinuously by heating the reaction mixture to the polymerization temperature. These temperatures are in the range from 40 to 150 ° C.
  • the monomers (A) are therefore added continuously or batchwise to the polymerizing mixture to the extent that the graft polymerization is readily controllable in the desired temperature range.
  • a type of addition of the monomers of component (A) is preferred, in which the compounds of component (B) or at least some of the compounds of component (B) are first combined with at least one monomer of group (a) in the polymerization reactor Submitted reactor and heated to the desired polymerization temperature with stirring. As soon as this temperature is reached, the remaining monomers of group (a) and optionally the monomers (b) and, if appropriate, (c) and the initiator are added over a period of about 1 to 10, preferably 2 to 8 hours and, if necessary, a controller.
  • capelan oil with 1% ditertiary butyl peroxide can be heated to 150 ° C. for 2 hours in a weak stream of N 2 and then acrylic acid is metered in at 150 ° C. in the course of 3 hours.
  • the grafted vegetable or animal oil is converted into an aqueous dispersion.
  • the dispersion can be made using conventional emulsifiers such as fatty alcohol ethoxylates, dodecylbenzene sulfonates, dioctyl sulfosuccinate or alkyl sulfonates can be carried out in suitable apparatus.
  • Emulsifier-free dispersion is particularly preferred by partially or completely neutralizing the carboxyl groups of the graft polymer with alkalis, alkaline earths, ammonia or amines and thus obtaining stable aqueous dispersions.
  • These dispersions have a solids content of 5 to 80% and preferably 20 to 70% and can thus be used directly for the treatment of leather and furskins.
  • the drying residue can be determined, for example, in a drying cabinet (2 h at 120 ° C.).
  • graft polymers to be used according to the invention it is possible to produce very soft leather without the addition of conventional liquors.
  • the water-repellent properties of hydrophobic leather are not adversely affected when these products are used.
  • the mechanical properties, such as tensile strength, as well as the light fastness and heat yellowing resistance of such leather, are very positively influenced by the use of these graft polymers.
  • the good fixation in the leather causes great resistance to extractability with solvents or water. This leads to so-called washable leathers, i.e. leathers that do not lose their properties such as softness, firmness and suppleness after washing; in contrast, this property is not to be expected for leathers that are greased with conventional licker.
  • aqueous dispersion to be used according to the invention preferably contains no additional emulsifiers.
  • leather and furs which are to be made hydrophobic and are treated with products containing emulsifiers, are known to have to undergo complex processes after treatment with these agents, e.g. Post-treatment with polyvalent metal salts, to make the emulsifiers in the leather or in the fur skins ineffective, i.e. to fix.
  • the graft polymer dispersions described above are suitable for the treatment of all conventional tanned hides.
  • the tanned skins are usually removed before the treatment. acidifies. They may have been stained before treatment. However, coloring can also be carried out only after the oiling has taken place according to the invention.
  • the tanned skins are expediently mixed with the aqueous dispersions in aqueous liquors, which can be obtained by diluting the graft polymer dispersions with water, at pH values of 4 to 10, preferably 5 to 8 and temperatures of 20 to 60, preferably 30 to 50 ° C. treated for a period of 0.1 to 5, in particular 0.5 to 2 h. This treatment takes place, for example, by drumming in a barrel.
  • the required amount of graft polymer dispersion, based on the shaved weight of the leather or the wet weight of the fur skins is 0.1 to 30, preferably 1 to 20,% by weight.
  • the fleet length i.e. the percentage weight ratio of the treatment liquor to the goods, based on the shaved weight of the leather or the wet weight of the fur skins, is usually 10 to 1000, preferably 30 to 150%, for fur skins 50 to 500%.
  • the pH of the treatment liquor is adjusted to a value of 3 to 5, preferably 3.5 to 4, by adding acids, preferably an organic acid such as formic acid.
  • the lung Behand ⁇ with the present invention aqueous dispersions to be used discontinuously before or after the retanning step the advertising used.
  • Example 2 Similar to Example 1, 100 g of capelan oil and 1 g of tert-butyl perethylhexanoate are heated to 150 ° and stirred for 1 hour. Then 10 g of maleic anhydride and 1 g of tert-butyl perethylhexanoate are added and the mixture is heated at 150 ° C. for 6 hours. After cooling, the mixture is diluted with 310 g of water and 7.2 g of 50% sodium hydroxide solution and the mixture is intensively dispersed for 10 minutes with the Ultra-Turrax. The dispersion obtained has a pH of 8.9, a drying residue of 25% and a Brookfield viscosity of 16 mPa-s at 23 ° C.
  • rapeseed oil are heated to 150 ° C. under a weak stream of N 2 . Then 20 g of acrylic acid (100%) and the solution of 1 g of tert-butyl perethylhexanoate in 10 g of rapeseed oil are uniformly metered in at 150 ° C. within 1 h. The mixture is then stirred at 150 ° for 2 h, a further 1 g of tert-butyl perethylhexanoate is added and the mixture is heated again at 150 ° C. for 2 h.
  • 100 g of the graft polymer thus obtained are diluted with 76 g of water and dispersed intensively for 10 minutes.
  • the white viscous dispersion has a pH of 3.5 and a drying residue of 55.9%.
  • Example 1 100 g of rapeseed oil and 1 g of tert-butyl perethylhexanoate are heated for 1 hour at 150 ° C. under a weak N 2 stream. Then 18 g of maleic anhydride and 1 g of tert-butyl perethylhexanoate are added and the mixture is heated at 150 ° C. for 6 h. It is then cooled and 105 g of the product are mixed with 90 g of water and 8 g of 50% sodium hydroxide solution and dispersed intensively for 10 minutes with the Ultra-Turrax. A homogeneous viscous dispersion is formed with a drying residue of 52.7% and a pH of 5.5.
  • Example 1 100 g of capelan oil are heated to 150 ° in a weak N 2 stream and then 20 g of acrylic acid and a solution of 1 g of tert-butyl perethylhexanoate in 10 g of capelan oil are uniformly added at 150 ° C. in the course of 1 h. The mixture is then heated for a further 1 h, a further 1 g of tert-butyl perethylhexanoate is added and the mixture is heated for a further 1 h. The mixture is then cooled and 103 g of the product, after adding 90 g of water and 9 g of 50% sodium hydroxide solution, are dispersed intensively for 10 minutes using Ultra-Turrax. The viscous homogeneous dispersion has a pH of 7.0 and the drying residue is 49.1%.
  • Example 6 20 g of methacrylic acid are used instead of acrylic acid. 115 g of the graft polymer obtained, 95 g of water and 14 g of 50% sodium hydroxide solution are intensively dispersed for 10 minutes with the Ultra-Turrax. The viscous dispersion has a pH of 7.1 and a drying residue of 51.2%.
  • Example 5 The product from Example 4 was used analogously to the procedure given in Example 3. The leather thus obtained showed soft and round grip properties.
  • Example 5 The product from Example 5 was used analogously to the procedure given in Example 1.
  • the leather thus obtained was characterized by a round, soft handle.
  • Example 6 The product from Example 6 was used analogously to the procedure given in Example 1. The result was similarly advantageous as in the previous examples.
  • Example 7 The product from Example 7 was used analogously to the procedure given in Example 3. The result was a soft leather with a comfortable grip.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne l'utilisation de polymères greffés, solubles ou dispersibles dans l'eau, d'huiles végétales et animales, obtenus par polymérisation par promoteurs radicalaires A) d'un monomère ou d'un mélange de monomères comprenant a) 20 à 100 % en poids d'acides carboxyliques monoéthyléniquement insaturés, et/ou d'acides sulfoniques monoéthyléniquement insaturés, et/ou d'acides phosphoniques monoéthyléniquement insaturés, ou de leurs sels alcalins, alcalino-terreux ou d'ammonium, b) 0 à 80 % en poids d'autres monomères monoéthyléniquement insaturés, copolymérisables avec les monomères (a), et c) 0 à 5 % en poids de monomères insaturés non conjugués ayant au moins deux doubles liaisons éthyléniques, en présence B) d'huiles végétales et/ou animales, dans un rapport pondéral A:B de (80 à 1) : (20 à 99), pour nourrir et fouler les cuirs et les peaux en poils. On obtient ainsi des cuirs souples d'un toucher agréable.
EP93915893A 1992-07-24 1993-07-13 Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils Expired - Lifetime EP0607388B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4224456A DE4224456A1 (de) 1992-07-24 1992-07-24 Verwendung von Pfropfpolymeren zum Fetten und Füllen von Leder und Pelzfellen
DE4224456 1992-07-24
PCT/EP1993/001831 WO1994002650A1 (fr) 1992-07-24 1993-07-13 Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils

Publications (2)

Publication Number Publication Date
EP0607388A1 true EP0607388A1 (fr) 1994-07-27
EP0607388B1 EP0607388B1 (fr) 1997-10-08

Family

ID=6463993

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93915893A Expired - Lifetime EP0607388B1 (fr) 1992-07-24 1993-07-13 Utilisation de polymeres greffes pour nourrir et fouler les cuirs et les peaux en poils

Country Status (7)

Country Link
US (1) US5620748A (fr)
EP (1) EP0607388B1 (fr)
JP (1) JPH06511284A (fr)
AU (1) AU662071B2 (fr)
DE (2) DE4224456A1 (fr)
ES (1) ES2108289T3 (fr)
WO (1) WO1994002650A1 (fr)

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DE4402029A1 (de) * 1994-01-25 1995-07-27 Basf Ag Wäßrige Lösungen oder Dispersionen von Copolymerisaten
DE19625984C2 (de) * 1996-06-28 1999-07-29 Stockhausen Chem Fab Gmbh Wäßrige Polymerdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung in der Lederherstellung
KR100346466B1 (ko) * 1999-12-06 2002-07-27 현대자동차주식회사 페이스트형 방음용 밀봉재 조성물
FR2836485B1 (fr) * 2002-02-28 2004-07-30 Coatex Sas Utilisations de polymeres acryliques greffes dans le domaine des substrats a base de collagene. substrats, peaux et cuirs ainsi obtenus
BR0318684A (pt) * 2003-12-25 2006-12-12 Council Scient Ind Res processo transformado para a fabricação de couros
US20060188729A1 (en) * 2005-02-22 2006-08-24 Kai-Volker Schubert Washable leather with repellency
FR2974578B1 (fr) * 2011-04-28 2015-10-30 Rhodia Operations Corps gras copolymerise, son procede de preparation et ses applications

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Also Published As

Publication number Publication date
AU4567993A (en) 1994-02-14
DE59307502D1 (de) 1997-11-13
DE4224456A1 (de) 1994-01-27
EP0607388B1 (fr) 1997-10-08
JPH06511284A (ja) 1994-12-15
US5620748A (en) 1997-04-15
AU662071B2 (en) 1995-08-17
ES2108289T3 (es) 1997-12-16
WO1994002650A1 (fr) 1994-02-03

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