EP0100493B1 - Procédé d'apprêtage du cuir ou cuirs synthétiques - Google Patents

Procédé d'apprêtage du cuir ou cuirs synthétiques Download PDF

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Publication number
EP0100493B1
EP0100493B1 EP83107140A EP83107140A EP0100493B1 EP 0100493 B1 EP0100493 B1 EP 0100493B1 EP 83107140 A EP83107140 A EP 83107140A EP 83107140 A EP83107140 A EP 83107140A EP 0100493 B1 EP0100493 B1 EP 0100493B1
Authority
EP
European Patent Office
Prior art keywords
weight
leather
copolymer
dispersion
methacrylamide
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
EP83107140A
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German (de)
English (en)
Other versions
EP0100493A1 (fr
Inventor
Karl Fischer
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
Priority claimed from DE19823228128 external-priority patent/DE3228128A1/de
Priority claimed from DE19833307431 external-priority patent/DE3307431A1/de
Application filed by BASF SE filed Critical BASF SE
Priority to AT83107140T priority Critical patent/ATE17023T1/de
Publication of EP0100493A1 publication Critical patent/EP0100493A1/fr
Application granted granted Critical
Publication of EP0100493B1 publication Critical patent/EP0100493B1/fr
Expired 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
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds

Definitions

  • the invention relates to a novel process for finishing leather or synthetic leather replacement material - leather is to be referred to in the following for the sake of simplicity - with a purely aqueous system which is free from organic solvents and in which certain aqueous polymer dispersions are used for priming and the finish are used.
  • the aim of a leather dressing (coating) is to give the tanned, greased and possibly colored raw leather the desired appearance, special gripping properties and the necessary fastness to use, such as. B. to give kink elasticity, water fastness and wet and dry rub fastness.
  • these properties could only be optimally achieved with systems that contained organic solvents.
  • the modern requirements regarding health and environmental protection made it necessary to realize leather finishing with purely aqueous systems. Previous attempts on this basis have so far not been satisfactory because at least one of the required properties has always not been achieved.
  • the object of the invention is a purely aqueous dressing process for leather, which should fully meet the above objectives.
  • the invention accordingly relates to a process for finishing leather or synthetic leather exchange material by applying a primer based on aqueous acrylic resin dispersions, intermediate drying and then applying a finish with an aqueous styrene-acrylate dispersion, which is characterized in that the primer a dispersion reaches the insert, the at least one copolymer a, which - based on the copolymer - 30 to 85 wt .-% of a C 2 to C 6 alkyl ester of (meth) acrylic acid, 1 to 8 wt .-% of a carboxyl-containing monomers and 7 to 65 wt .-% of at least one copolymerizable with the aforementioned monomers from the group of acrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinyl acetate and styrene, copolymerized, and a copolymer b, which - based on the copolymer - 50 to 90 wt
  • the primer is carried out with a dispersion which contains at least one copolymer a and one copolymer b.
  • a and b are in a ratio of 2 to 5: 1, preferably 2 to 4.5: 1, and together they are present in the dispersion in an amount of 30 to 70, preferably 35 to 60% by weight.
  • the copolymer a is a typical acrylic resin known in terms of its composition. It contains 30 to 85, preferably 60 to 75% by weight of a C 2 -C 6 -alkyl ester of (meth) acrylic acid, preferably ethyl, n-propyl or n-butyl acrylate, as a monomer unit. It also contains 1 to 8% by weight of a monomer containing carboxyl groups, such as (meth) acrylic acid, crotonic acid, maleic acid or acrylamidoglycolic acid. Up to 2 to 5% by weight of these comonomers are preferably copolymerized in the copolymer; acrylic acid is preferred as the comonomer.
  • Comonomers which can be copolymerized with the abovementioned are also present in amounts of 7 to 65, preferably 20 to 38% by weight, and acrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinyl acetate and / or styrene are to be mentioned here in particular .
  • the copolymer b contains 50 to 90, preferably 55 to 70% by weight of vinylidene chloride as main constituents. It also contains a C 2 -C 4 -alkyl ester of (meth) acrylic acid in an amount of 10 to 50, preferably 25 to 40% by weight. Ethyl or butyl acrylate is preferably used here.
  • N-methylol (meth) acrylamide which is copolymerized in amounts of 1 to 5, preferably 1 to 3,% by weight is particularly worth mentioning as the crosslinking comonomer.
  • copolymerized (b) (meth) acrylamide can optionally be copolymerized in the copolymer, specifically 1 to 5, preferably 1 to 3,% by weight.
  • the copolymer a can consist of a mixture of two copolymers according to definition a, based on the total quantity, exist. If a second copolymer is used, a copolymer of the composition according to a with proportions of 65 to 85% by weight of one of the abovementioned alkyl esters of (meth) acrylic acid is preferred. This softens the primer.
  • the dispersion for the subsequent finishing of the primed leather contains a salt of a divalent metal, such as zinc, cadmium, calcium or magnesium, which causes the polymers contained therein to ionize.
  • a divalent metal such as zinc, cadmium, calcium or magnesium
  • the chlorides, sulfates, acetates, nitrates, oxalates or carbonates are expediently used as salts.
  • zinc and magnesium zinc oxide or magnesium oxide can also be used.
  • the advantageous amounts of metal compound are 0.3 to 3, preferably 0.5 to 2% by weight, based on the aforementioned dispersion.
  • the copolymer c used here contains 20 to 40% by weight of styrene, 50 to 75% by weight of at least one C 1 to C 6 alkyl ester of (meth) acrylic acid, preferably methyl, ethyl and / or n Butyl acrylate, 1 to 10% by weight of (meth) acrylic acid, preferably 2 to 9% by weight, and 1 to 5, preferably 2 to 4% by weight of a monomer capable of covalent crosslinking, such as N - methylol ( meth) acrylamide.
  • the aqueous dispersion of the copolymer c to be used in the finish expediently has a content of 10 to 50, preferably 15 to 30,% by weight.
  • the dispersion c used for finishing contains, based on the total weight, 0.5 to 20, preferably 2 to 8% by weight of shellac modified with acrylates and 0.5 to 3% by weight.
  • additives based on the dispersion, in an amount of 1 to 10, preferably 1 to 6,% by weight of high-boiling polyglycols, phthalic acid esters, ethylene glycol, waxes of natural or synthetic origin as plasticizers, and also fungicides, such as the Na salt of diazenium dioxide cyclohexane.
  • these additives also apply to the primer dispersion, as can be seen from the examples.
  • this simplification has the consequence that leather prepared by this process is resistant to amien in addition to the known usage fastnesses. What is meant is that the applied film does not yellow under the influence of amines. This advantageous result of the amine resistance while maintaining the other usage fastnesses, such as water resistance, elasticity, adhesion to leather, light fastness and hot storage stability, were not predictable.
  • the amine resistance of the leather preparation according to the invention to free amines is of particular advantage for shoe leather in shoe manufacture when foaming polyurethane soles on the upper leather and, for example, in polyurethane foam fillings for furniture leather.
  • the leather is finished with the dispersions to be used according to the invention in a manner which is conventional per se.
  • the primer dispersion can also be applied in several steps, each interrupted by intermediate drying.
  • the dispersion for the final finish is then applied in a customary manner in amounts of 10 to 30 g of solid per square meter of leather. It is first dried at 60 to 80 ° C, ironed at 140 to 170 ° C and optionally ironed at 80 to 100 ° C under reduced pressure.
  • pigment preparations and / or dyes can be used in the primer and finish dispersion for the primer. It is advantageous to add 1 to 5 g of pigment preparation and / or commercial dye - based on 10 g of the solids present in the dispersions.
  • Hot ironing should be understood to mean that e.g. B. the leather is ironed at a temperature of 90 to 180 ° C, preferably at 120 to 170 ° C, with a conventional continuous ironing machine.
  • the leather sprayed in this way was dried at 70 ° C. after each spray application and ironed in at 70 ° C. and 50 bar after the first spray application.
  • Application rate 45 g solids / m 2 .
  • the preparation was sprayed on by means of a compressed air gun with two spraying jobs, intermediate and final drying at 70 ° C, then ironed at 170 ° C on the continuous ironing machine.
  • the leather obtained has the sensory properties desired for a shoe upper leather (feel, gloss, etc.) and also fulfills the fastness properties required in practice, e.g. Water resistance, elasticity and amine resistance.
  • Cowhide nappa leather for clothing was coated with the following primer preparation:
  • the leather treated in this way was intermediate dried at 70 ° C. after each of the three spray applications.
  • the leather was then sprayed with the following finish preparation:
  • the leather obtained showed all the properties required for clothing, such as Handle, abrasion resistance or waterfastness.
  • Cowhide for upholstery purposes was similarly coated with a primer mixture of the following composition (order quantity:
  • Two spraying jobs each dried at 70 ° C, ironed at 150 ° C (continuous ironing machine) and ironed at 90 ° C on the hydraulic ironing machine.
  • the leather thus obtained has all the properties desired for upholstered leather, such as. B. coefficients of friction, elasticity, light fastness, abrasion resistance, amine resistance and hot iron fastness.
  • the leather was coated once with this primer mixture with the puddle board, then dried at 70 ° C, ironed at 70 ° C, plushed again and with intermediate drying sprayed at 70 ° C with two spray jobs (air pressure gun).
  • Application quantity 80 g solid / m 2 .
  • the primed leather was then coated with the following finish: Application quantity: 30 g / m 2 .
  • This preparation was applied using a compressed air gun with two spraying jobs, dried at 70 ° C and ironed at 100 ° C on the continuous ironing machine.
  • the leather obtained has the properties desired for upper leather. It is lightfast, amine-resistant, waterproof and has sufficient elasticity.
  • the primed leather was then finished with a preparation of the following composition:
  • the leather obtained is waterproof and mechanically stressable without the finish peeling off.
  • the leather obtained showed all the properties desired for clothing purposes in terms of grip, abrasion resistance and waterfastness.
  • Goat leather was similarly made with a mixture of (30 g / m 2 )
  • the leather obtained has all the properties that are desired for handbags and briefcases.

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)

Claims (1)

  1. Procédé de corroyage du cuir, ou matériau synthétique de remplacement du cuir, par application d'une couche de fond à base de dispersions aqueuses de résine acrylique, séchage intermédiaire puis enduction d'un apprêt avec une dispersion aqueuse de styrène-acrylate, caractérisé par le fait que, pour la couche de fond, on met en oeuvre une dispersion qui contient, en polymérisation, au moins un copolymérisat a, qui contient - par rapport au copolymérisat - 30 à 85% en poids d'un (méth)acrylate d'alkyle en C2 à C6, 1 1 à 8% en poids d'un monomère à groupes carboxyle et 7 à 65% en poids d'au moins un monomère, copolymérisable avec les susdits monomères, du groupe acrylonitrile, acrylamide, méthacrylamide, chlorure de vinyle, acétate de vinyle et styrène, et un copolymérisat b qui contient - par rapport au copolymérisat ― 50 à 90% en poids de chlorure de vinylidène, 10 à 50% en poids d'un (méth)acrylate d'alkyle en C2 à C4 et, comme comonomère, 1 à 5% en poids de N-méthylol-(méth)acrylamide, portant un groupe approprié pour la réticulation du copolymérisat, et éventuellement 1 à 5% en poids de (méth)acrylamide, ou qui contient, en dispersion, la composition de 50 à 90% en poids de chlorure devinyle et 10 à 50% en poids d'un (méth)acrylate d'alkyle en Ci à C4, ainsi que 0 à 5% en poids de (méth)acrylamide, le rapport entre copolymérisat a et copolymérisat b étant de 2 à 5/1, et on utilise, comme apprêt, une dispersion contenant des ions de métaux divalents, et qui contient, en dispersion, un copolymérisatc qui contient, en polymérisation ― par rapport au copolymérisat ― 20 à 40% en poids de styrène, 50 à 75% en poids d'au moins un (méth)acrylate d'alkyle en Ci à Cs, 1 à 10% en poids d'acide (méth)acrylique et 1 à 5% en poids de méthylol-(méth)acrylamide, portant un groupe approprié pour la réticulation du copolymérisat.
EP83107140A 1982-07-28 1983-07-21 Procédé d'apprêtage du cuir ou cuirs synthétiques Expired EP0100493B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83107140T ATE17023T1 (de) 1982-07-28 1983-07-21 Verfahren zum zurichten von leder oder synthetischem lederaustauschmaterial.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3228128 1982-07-28
DE19823228128 DE3228128A1 (de) 1982-07-28 1982-07-28 Verfahren zum zurichten von leder oder synthetischem lederaustauschmaterial
DE3307431 1983-03-03
DE19833307431 DE3307431A1 (de) 1983-03-03 1983-03-03 Verfahren zum zurichten von leder oder synthetischem lederaustauschmaterial

Publications (2)

Publication Number Publication Date
EP0100493A1 EP0100493A1 (fr) 1984-02-15
EP0100493B1 true EP0100493B1 (fr) 1985-12-18

Family

ID=25803337

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83107140A Expired EP0100493B1 (fr) 1982-07-28 1983-07-21 Procédé d'apprêtage du cuir ou cuirs synthétiques

Country Status (4)

Country Link
US (1) US4491612A (fr)
EP (1) EP0100493B1 (fr)
CA (1) CA1209863A (fr)
DE (1) DE3361561D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0437742B1 (fr) * 1990-01-16 1996-02-28 BASF Aktiengesellschaft Compositions de polymère aqueux

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3610576A1 (de) * 1986-03-27 1987-10-01 Bayer Ag Acrylatbinder und seine verwendung zum zurichten von leder
DE3736475A1 (de) * 1987-10-28 1989-05-11 Basf Ag Verfahren zum zurichten von leder
AU717402B2 (en) * 1995-09-15 2000-03-23 Rohm And Haas Company Method for coating leather
WO1997035927A1 (fr) * 1996-03-26 1997-10-02 Basf Aktiengesellschaft Compositions stables de colorants
US5723182A (en) * 1996-08-27 1998-03-03 Rohm And Haas Company Method for coating leather
AUPO216396A0 (en) 1996-09-06 1996-10-03 Ici Australia Operations Proprietary Limited Stain resistant water-borne paint
US20040245490A1 (en) * 2001-09-28 2004-12-09 Holger Schopke Top coating composition for leather
RU2198224C1 (ru) * 2002-01-10 2003-02-10 Общество с ограниченной ответственностью "Легхим" Состав для отделки натуральной кожи
US6849682B2 (en) * 2002-09-30 2005-02-01 Omnova Solutions Inc. VOC containment coating, methods and articles
RU2229521C1 (ru) * 2003-06-11 2004-05-27 Федеральное государственное унитарное предприятие "Центральный научно-исследовательский институт кожевенно-обувной промышленности" Способ обработки натуральных кож
DE102004032766A1 (de) * 2004-07-06 2006-02-09 Röhm GmbH & Co. KG Konzentrierte wässrige Methacrylamidlösung unter Zugabe von Methacrylsäure
JP6713046B2 (ja) * 2015-12-18 2020-06-24 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ クロムフリー革の再なめし

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2884336A (en) * 1955-01-27 1959-04-28 Rohm & Haas Methods for producing coated leather and the products thereof
FR1275872A (fr) * 1960-12-09 1961-11-10 Rohm & Haas Cuirs apprêtés et leur procédé de fabrication
NL278787A (fr) * 1961-05-24 1900-01-01
US3403119A (en) * 1964-10-19 1968-09-24 Staley Mfg Co A E Polymeric coating composition containing a metal salt of an organic carboxylic acid
US3919451A (en) * 1973-07-09 1975-11-11 Rohm & Haas Method for finishing leather and leather substitutes
US4256809A (en) * 1979-02-02 1981-03-17 Rohm And Haas Company Ambient or low-temperature curable coatings for leather and other flexible substrates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0437742B1 (fr) * 1990-01-16 1996-02-28 BASF Aktiengesellschaft Compositions de polymère aqueux

Also Published As

Publication number Publication date
DE3361561D1 (en) 1986-01-30
US4491612A (en) 1985-01-01
EP0100493A1 (fr) 1984-02-15
CA1209863A (fr) 1986-08-19

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