EP0029170B2 - Verfahren zum Zurichten von Spaltleder und geschliffenem Leder durch Behandlung mit Kautschuklatices. - Google Patents

Verfahren zum Zurichten von Spaltleder und geschliffenem Leder durch Behandlung mit Kautschuklatices. Download PDF

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Publication number
EP0029170B2
EP0029170B2 EP80106796A EP80106796A EP0029170B2 EP 0029170 B2 EP0029170 B2 EP 0029170B2 EP 80106796 A EP80106796 A EP 80106796A EP 80106796 A EP80106796 A EP 80106796A EP 0029170 B2 EP0029170 B2 EP 0029170B2
Authority
EP
European Patent Office
Prior art keywords
leather
weight
parts
dressing
latex
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.)
Expired
Application number
EP80106796A
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German (de)
English (en)
French (fr)
Other versions
EP0029170B1 (de
EP0029170A1 (de
Inventor
Ferdinand Dr. Heins
Leo Dr. Tork
Wolfgang Höhne
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.)
Bayer AG
Original Assignee
Bayer AG
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Publication date
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Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0029170A1 publication Critical patent/EP0029170A1/de
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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
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/4935—Impregnated naturally solid product [e.g., leather, stone, etc.]

Definitions

  • the present invention relates to a process for finishing split leather and sanded leather with carboxylated rubber latices from conjugated dienes, vinyl aromatics and / or (meth) acrylonitrile by reaction with oxides and / or hydroxides of divalent metals.
  • Aqueous copolymer dispersions are generally used as binders. These copolymer dispersions are polyacrylate dispersions, dispersions of copolymers _ of vinyl acetate with acrylic esters or ethylene or synthetic rubber dispersions.
  • pigments are of inorganic and organic provenance, for example iron oxide, titanium dioxide, kaolin, azo pigments and phthalocyanines.
  • the formulations may contain conventional thickeners, e.g. B. those based on cellulose such as carboxymethyl cellulose, polyvinyl alcohols, poly-N-vinyl pyrrolidones, polyacrylic acid and its salts and casein.
  • copolymer dispersions are satisfactory when used on full-grain and sanded leathers, but not on split leathers. Preparations on split leather, especially for upper leather, show when using the above. Copolymer dispersions have poor embossability as well as insufficient fastness properties, especially insufficient dry and wet kink strengths, poor layer adhesion and poor cold flexibility.
  • French patent specification 1 197 476 describes a process for the heat ironing of leather by treatment with polymer dispersions containing carboxylic acid groups in the presence of zinc compounds.
  • the hot ironing strength of the dressing can be improved, but coverage, surface calmness, shine, fullness and grip are deteriorated.
  • adhesion problems arise between the individual layers as a result of networking. The upper layer is insufficiently anchored to the lower layer, so that poor wet strength and wet adhesion are obtained.
  • the rubber latex is preferably reacted with 1 to 20% by weight, based on solid rubber, of one or more oxides and / or hydroxides of divalent metals.
  • the British patent specification 900 591 in Example 6 describes the preparation of a copolymer from methacrylamide, butyl acrylate, 2-chlorobutadiene and styrene, which is suitable as a leather finishing agent and in which the polymerization is interrupted at 95% conversion, but is then carried out after further addition of monomers completed the polymerization.
  • the German patent specification 1 103 509 describes the production of chloroprene polymers, the polymerization being carried out in one Sales of 80% is canceled.
  • the products are said to be suitable for the production of films and impregnations on leather.
  • chloroprene polymers have not found their way into the technology of leather finishing for various reasons.
  • a re-creation of Example 4 shows that the product, used for leather finishing, has poor dry and wet buckling strength.
  • Examples of a, ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids are: acrylic acids, methacrylic acid, itaconic, fumaric and maleic acids and monoesters of these dicarboxylic acids, such as, for example, B. monoalkyl itaconate, fumarate and maleate.
  • anionogenic emulsifiers are salts of higher fatty acids and resin acids, higher fatty alcohol sulfates, higher alkyl sulfonates and alkyl aryl sulfonates and their condensation products with formaldehyde, higher hydroxyalkyl sulfonates, salts of sulfosuccinic acid esters and sulfated ethylene oxide adducts.
  • cationic emulsifiers are salts of alkyl-, aryl- and alkylarylamines with inorganic acids, salts of quaternary ammonium compounds and alkylpyridinium salts.
  • reaction products of ethylene oxide with isononyl, dodecyl, tetradecyl mercaptan and higher alkyl mercaptans and higher alkyl thiophenols or similar reaction products of etherified or esterified polyhydroxy compounds with a longer alkyl chain such as sorbitol monostearate may be mentioned as examples.
  • the compounds given as examples are reacted with 4-60 or more moles of ethylene oxide.
  • block copolymers of ethylene oxide and propylene oxide with at least one mole of ethylene oxide can also be used here.
  • Suitable initiators are e.g. B. inorganic peroxo compounds such as hydrogen peroxide, sodium, potassium or ammonium peroxodisulfate, peroxocarbonates and borate peroxy hydrates, also organic peroxo compounds such as acyl hydroperoxides, diacyl peroxides, alkyl hydroperoxides, dialkyl peroxides and esters such as tert-butyl perbenzoate.
  • the amount of initiator is generally within the limits of 0.01-5% by weight, based on the total of the monomers used.
  • the inorganic or organic peroxo compounds given as examples can also be used in a known manner in combination with suitable reducing agents.
  • suitable reducing agents are: sulfur dioxide, alkali disulfites, alkali and ammonium hydrogen sulfites, thiosulfate, dithionite and formaldehyde sulfoxylate, furthermore hydroxylamine hydrochloride, hydrazine sulfate, iron (11) sulfate, tin (II) chloride, titanium (III) sulfate, hydroquinone, Glucose, ascorbic acid and certain amines.
  • Chain transfer agents such as B. tetrabromomethane, tetrabromethane, lower and higher alcohols, higher alkyl mercaptans and dialkyldixanthates can also be used in the polymerization.
  • the type and amount of chain transfer agents depend, among other things. on the effectiveness of the chain transfer agent and on the amount of diene used. The choice and the amount of the chain transfer agent is of particular importance because both the layer adhesion of the leather finishes made from the rubber latices and their kink resistance in the dry and wet state can be optimized within certain limits.
  • Suitable chain terminators are, for example, sodium dimethyldithiocarbamate, hydroxylamine, dialkylhydroxylamine, hydrazine hydrate and hydroquinone.
  • the latex is freed of residual monomers in a manner known per se.
  • latices can be produced whose solids content is between 1 and 65% by weight. However, latices with solids contents between 30 and 50% by weight are usually used.
  • the synthetic rubber latices according to the invention are in themselves not suitable for dressing leather, but only lead to excellent technical advantages in combination with oxides and / or hydroxides of divalent metals, which react with the carboxyl groups of the copolymer.
  • Suitable oxides of divalent metals are, for example, barium, magnesium, calcium and zinc oxide, the latter being particularly preferred. These oxides are obtained by calcining the corresponding finely divided carbonates.
  • the corresponding hydroxides can be precipitated from the aqueous solutions of the corresponding salts by adding alkali or by reacting the oxides with water.
  • the leather can therefore also be prepared by using aqueous solutions of the divalent metals and producing the corresponding hydroxides in situ by adding alkali.
  • the oxides and / or hydroxides of divalent metals are additionally organic solvents such as alcohols, e.g. B. ethyl, n-propyl and isopropyl alcohol or ethylene glycol monoethyl ether or ketones such as acetone and methyl ethyl ketone, natural or synthetic oils such as claw oil, peanut oil or Vietnamese red oil in free and / or emulsified form and suitable defoamers added.
  • organic solvents such as alcohols, e.g. B. ethyl, n-propyl and isopropyl alcohol or ethylene glycol monoethyl ether or ketones such as acetone and methyl ethyl ketone, natural or synthetic oils such as claw oil, peanut oil or Turkish red oil in free and / or emulsified form and suitable defoamers added.
  • the processing can be done on full-grain, sanded and split leather or leather fiber materials of any provenance.
  • the finishes are applied to the leather in a manner known per se using the copolymer latices according to the invention, pigment preparations of the type mentioned above and other additives.
  • the dressings can be applied by casting, knife coating, brushing, spraying, brushing or plush processes. The amount of finishing depends on the type and pretreatment of the leather and can be easily determined by preliminary tests.
  • the primer is carried out in one or more orders. Hot, strong intermediate ironing or scar embossing ensures good fusion and thus a good finish of the primer. Then an upper top coat can be applied with the same liquor.
  • the viscosity of the rubber latices can be regulated by adding thickeners of the type mentioned at the outset, so that the penetration can easily be reduced by increasing the viscosity.
  • the thickened rubber latices are particularly suitable for dressing split leather due to the resulting higher filling effect and the improved film-forming ability.
  • polyurethane varnishes, collodion varnishes or collodion varnish emulsions of the oil-in-water and water-in-oil type and aqueous polyacrylate or polyurethane dispersions which are applied by spraying and casting processes are suitable.
  • a mixture of 18,000 g of water, 5000 g of butadiene- (1,3), 3,000 g of acrylonitrile, 1,700 g of styrene, 333 g of 90% methacrylic acid and 50 is in a 40-liter stainless steel autoclave with a cross bar stirrer g of tert-dodecyl mercaptan in the presence of 200 g of a sodium sulfonate of a mixture of long-chain paraffin hydrocarbons with an average chain length of 15 carbon atoms as emulsifier and 5 g of 70% tert-butyl hydroperoxide and 2.5 g of sodium formaldehyde sulfoxylate dihydrate (Rongalit C) as redox initiator system at 35 ° C polymerized until a solids concentration of 20% is reached.
  • a solution of 100 g of a reaction product of isononylphenol with 20 moles of ethylene oxide and 2.5 g of Rongalit C in 500 g of water is then pressed in and the polymerization is continued at 35 ° C. After a solids concentration of 31% (approx. 86% conversion) has been reached, the polymerization is stopped with a solution of 200 g of 25% diethylhydroxylamine in 200 g of water.
  • the latex A obtained is freed of residual monomers and has a solids concentration of 31%.
  • a mixture of 18,000 g of water, 500 g of butadiene (1,3), 3,000 g of acrylonitrile, 1 g of styrene, 100 g of itaconic acid and 50 g of tert-dodecyl mercaptan are mixed with 200 g of a sodium sulfonate using a mixture of long-chain paraffinic hydrocarbons a medium one Chain length of 15 carbon atoms as an emulsifier and 5 g of 70% tert-butyl hydroperoxide and 2.5 g of sodium formaldehyde sulfoxylate (Rongalit C) as an initiator system in a 40 liter stainless steel autoclave with a crossbar stirrer at 35 ° C to a solids content of Polymerized 20%.
  • a sodium sulfonate using a mixture of long-chain paraffinic hydrocarbons a medium one Chain length of 15 carbon atoms as an emulsifier and 5 g of 70%
  • crosslinking pastes are used to carry out the dressing process according to the invention, the production of which is described below by way of example.
  • 8 parts of zinc oxide, which was obtained by calcining fine zinc carbonate, are introduced into 16 parts of an aqueous claw oil emulsion, prepared by emulsifying crude claw oil in equal parts of water with the aid of a nonionic alkyl polyglycol ether at 90 ° C in the course of 10 minutes using a high-speed stirrer, 6 Parts of a 50% aqueous Turkish red oil solution and 3 parts of an addition product of about 20 moles of ethylene oxide with 1 mole of benzylphenylphenol.
  • the mixture is stirred intensively for a further 15 minutes.
  • the split leather or polished vachettes to be treated are given 1 to 2 applications by means of a brush, plush board, airless gun, spraying or casting machine.
  • the total application amount is approximately 150-300 g / m 2 .
  • the leather is ironed or scarred at 100 ° C and 350 bar with a 2 - 5 second delay.
  • the upper top coat is applied with the same liquor (order 100 - 200 g / m 2 ).
  • a common collodion varnish is applied as a finish by spraying or pouring.
  • the dressing obtained has the advantageous properties specified in the description.

Landscapes

  • 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)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
EP80106796A 1979-11-17 1980-11-05 Verfahren zum Zurichten von Spaltleder und geschliffenem Leder durch Behandlung mit Kautschuklatices. Expired EP0029170B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2946435A DE2946435C2 (de) 1979-11-17 1979-11-17 Verfahren zum Zurichten von Leder durch Behandlung mit Kautschuklatices
DE2946435 1979-11-17

Publications (3)

Publication Number Publication Date
EP0029170A1 EP0029170A1 (de) 1981-05-27
EP0029170B1 EP0029170B1 (de) 1983-12-07
EP0029170B2 true EP0029170B2 (de) 1989-08-23

Family

ID=6086220

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80106796A Expired EP0029170B2 (de) 1979-11-17 1980-11-05 Verfahren zum Zurichten von Spaltleder und geschliffenem Leder durch Behandlung mit Kautschuklatices.

Country Status (7)

Country Link
US (1) US4330597A (enrdf_load_stackoverflow)
EP (1) EP0029170B2 (enrdf_load_stackoverflow)
JP (1) JPS5684800A (enrdf_load_stackoverflow)
BR (1) BR8007487A (enrdf_load_stackoverflow)
CA (1) CA1142817A (enrdf_load_stackoverflow)
DE (2) DE2946435C2 (enrdf_load_stackoverflow)
ES (1) ES8306507A1 (enrdf_load_stackoverflow)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3229150C2 (de) * 1982-08-04 1986-04-10 Helmut 6780 Pirmasens Schaefer Verfahren und Vorrichtung zum Zurichten von Spaltleder
DE3318219A1 (de) * 1983-05-19 1984-11-22 Basf Ag, 6700 Ludwigshafen Verfahren zum zurichten von leder mit einer synthetischen carboxylierten kautschuk-dispersion
DE3436751C2 (de) * 1984-10-06 1987-04-02 Philipp 3000 Hannover Schaefer Vorrichtung zum Zurichten von Spaltleder
US5043396A (en) * 1988-12-28 1991-08-27 Nippon Zeon Co., Ltd. Novel crosslinked polymer having shape memorizing property, method of its use, and molded article having shape memory
DE3931039A1 (de) * 1989-09-16 1991-03-28 Basf Ag Verwendung von copolymerisaten auf basis von langkettigen ungesaettigten estern und ethylenisch ungesaettigten carbonsaeuren zum hydrophobieren von leder und pelzfellen
EP0562088B1 (en) * 1991-10-11 1998-03-25 Ansell Perry Inc. Rubber articles having a modified polymer layer of ether and ester units
US5570475A (en) * 1991-10-11 1996-11-05 Ansell Perry Inc. Surgeon's glove having improved donning properties
US6011104A (en) * 1998-01-20 2000-01-04 Udy; Joseph D. Footware dressings incorporating fluorocarbons
MX340625B (es) 2011-02-09 2016-07-18 Lubrizol Advanced Mat Inc Composicion de recubrimiento.

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE821997C (de) * 1949-04-05 1951-11-22 Bayer Ag Zurichtung von Leder
FR1197476A (fr) * 1957-07-01 1959-12-01 Bayer Ag Procédé de finissage du cuir
NL246582A (enrdf_load_stackoverflow) * 1958-12-19
DE1174937B (de) * 1959-06-04 1964-07-30 Bayer Ag Verfahren zum Zurichten von Leder
DE1224428B (de) * 1960-04-28 1966-09-08 Bayer Ag UEberzugs- und Impraegniermittel auf der Grundlage von waesserigen Mischpolymerisatemulsionen
US3344103A (en) * 1965-03-08 1967-09-26 Goodrich Co B F Self curing synthetic latices
GB1126834A (en) * 1966-04-09 1968-09-11 Polymer Corp Latex-based compositions

Also Published As

Publication number Publication date
DE3065841D1 (en) 1984-01-12
EP0029170B1 (de) 1983-12-07
ES496847A0 (es) 1983-06-01
ES8306507A1 (es) 1983-06-01
JPS5684800A (en) 1981-07-10
US4330597A (en) 1982-05-18
DE2946435A1 (de) 1981-05-21
CA1142817A (en) 1983-03-15
EP0029170A1 (de) 1981-05-27
BR8007487A (pt) 1981-06-02
JPS6131760B2 (enrdf_load_stackoverflow) 1986-07-22
DE2946435C2 (de) 1982-02-18

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