WO2003023071A1 - Agent d'appretage pour le cuir - Google Patents

Agent d'appretage pour le cuir Download PDF

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Publication number
WO2003023071A1
WO2003023071A1 PCT/EP2002/010088 EP0210088W WO03023071A1 WO 2003023071 A1 WO2003023071 A1 WO 2003023071A1 EP 0210088 W EP0210088 W EP 0210088W WO 03023071 A1 WO03023071 A1 WO 03023071A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
parts
leather
acrylamide
alkanols
Prior art date
Application number
PCT/EP2002/010088
Other languages
German (de)
English (en)
Inventor
Holger SCHÖPKE
Stefan Adams
Helfried Scheidl
Original Assignee
Basf Aktiengesellschaft
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 Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to US10/488,106 priority Critical patent/US20040245490A1/en
Priority to EP02781181A priority patent/EP1427863A1/fr
Publication of WO2003023071A1 publication Critical patent/WO2003023071A1/fr

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
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen

Definitions

  • the present invention relates to a finishing agent for leather, a process for its production and its use and leather treated accordingly.
  • the first coating is the primer, consisting of pigments, binders and auxiliaries to achieve adhesion for the entire finishing layer.
  • the second layer is a top layer, which is usually set a little harder than the primer. It conveys the desired look and equalizes the leather surface.
  • the third layer is the finish (top layer). It determines the final appearance and the feel of the leather surface and significantly influences the authenticity properties of the finish. Brushing, spraying, casting, printing, laminating and coating are known as application methods for the coatings.
  • Solvent-based nitrocellulose solutions or water-based polyurethane or nitrocellulose emulsions are frequently used as the third layer, cf. Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 1998 Electronic Release, chapter "Leather-Finishing and Coating (Eckhardt Heidemann)", section 11.1. It is said that the finish determines the final properties of the leather. The finish should be as hard and compact as possible to have the desired rub resistance, but on the other hand should be as soft as necessary so that the leather can be bent and stretched without breaking. Some topcoats contain additives based on silicon dioxide or wax for special matting effects.
  • the finish / top layer is responsible for the resistance to mechanical influences, water and dust.
  • VOC Volatile Organic Compounds
  • EP-A-0 437 742 relates to aqueous polymer preparations which can be used in particular as binders for coatings on leather or leather exchange materials.
  • the preparations contain no additional crosslinking agents or metal ions and are made up of two different poly (meth) acrylate dispersions which carry free carboxylic acid groups.
  • the agents also contain external plasticizers, emulsifiers and water. They can also contain polyurethanes and waxes.
  • EP-A-0 563 819 relates to processes for treating leather.
  • Products made from graft polymers based on (meth) acrylate are used. It is stated that polymer products based on polymethacrylate have been used increasingly both for impregnation and priming and, more recently, for the final coating of leather.
  • graft bases based on ethyl, butyl and 2-ethylhexyl acrylate are preferably used, onto which ethyl, butyl and isobutyl methacrylic acid esters are preferably grafted.
  • the finished coated leather is preferably tempered between 60 and 120 ° C.
  • the preparation of the graft polymers is complex and cost-intensive.
  • the object of the present invention is to provide an aqueous, low-VOC or solvent-free finishing agent based on (meth) acrylate copolymer which fully meets today's quality requirements for a leather top coating and avoids the disadvantages of the known finishing agents.
  • the finishing agent should be able to replace the known nitro lacquer emulsions in whole or in part without there being any loss of quality in the leather surface.
  • finishing agent should preferably be combinable or mixable with polyurethane finishing agents in a wide range.
  • the object is achieved according to the invention by a finishing agent for leather containing
  • the total amount of AI, A2 and optionally A3 and A4 being 100% by weight
  • the finishing agent is free from plasticizers and synthetic waxes. It has been found according to the invention that (Mefh) acrylate copolymers, whose films cast from aqueous dispersion at room temperature are brittle and not elastic, show an excellent performance profile when dressing leather as a finishing agent. In particular, they deliver balanced results in the quality requirement profile of grip, smoothness, gloss, scratch resistance, wet and dry rub resistance and flexo values. Especially in the shoe upper leather finishing all desired requirements have to be fully met.
  • the finishing agents according to the invention thus form a full substitute for the nitrocellulose lacquers, the use of which could not be dispensed with in spite of the VOC problem.
  • finishing agents according to the invention can advantageously be blended or combined with the polyurethane binders and crosslinking agents used there without loss of quality for the production of high-priced and high-quality leathers, for example for the furniture or car upholstery leather market.
  • finishing agents according to the invention can be mixed in a wide range with commercially available polyurethane topcoats. Mixtures of, for example, 50 parts: 50 parts solid on solid have similarly good rub fastness and flexometer values in the final coating as the pure polyurethane topcoats.
  • the use of the finishing agents according to the invention in combination with polyurethane binders can increase the gloss of the final coatings.
  • Polyurethane binders are sometimes used for the highest stresses in surface preparation with crosslinking agents, for example crosslinking agents containing isocyanate groups.
  • crosslinking agents for example crosslinking agents containing isocyanate groups.
  • the same amounts of crosslinking agent calculated on the solids content can be used, regardless of the proportion of the copolymers A used according to the invention.
  • finishing agents according to the invention have a better property profile for top coatings than the graft polymers known from EP-A-0 563 819. Compared to EP-A-0 437 742, the VOC problem can be avoided and the compatibility with other systems has been increased.
  • the copolymer A used according to the invention is preferably composed of al) 55 to 70% by weight methyl methacrylate or methyl methacrylate / butyl methacrylate a2) 40 to 25% by weight butyl acrylate or butyl acrylate / ethyl acrylate a3) 0.5 to 2% by weight acrylic acid or methacrylic acid a4) 0.1 to 2% by weight .-% acrylamide or methacrylamide
  • the dispersed copolymer A can have a single or multi-phase structure.
  • it can be produced by known emulsion polymerization processes or step polymerization processes. Suitable processes are described in the appended examples, see copolymer A corresponding to examples 1 to 6.
  • the property profile of the finishing agent is influenced by the composition of the copolymer A.
  • the gloss and transparency of the top coat can be adjusted by choosing the emulsion feed procedure or a step procedure in the copolymerization.
  • the other properties such as wet and dry rub fastness and the flexometer values are, however, less influenced by the driving style.
  • a step-by-step procedure is advantageously chosen.
  • the one-stage copolymer A preferably has a glass transition temperature of + 20 ° C. to 60 ° C.
  • two transitions at temperatures in the range from 20 to 40 ° C. and 60 to 120 ° C. are particularly preferably found. Transitions at about 30 ° C. and 100 to 110 ° C. are particularly preferred.
  • a crosslinker can also be used to prepare the copolymers A.
  • Suitable crosslinkers are, for example, butanediol diacrylate or allyl methacrylate in stage 1 or N-methylol-acrylamide or N-methylol-methacrylamide in stages 1 and 2.
  • the use of a crosslinker can also be dispensed with. This also applies to two-phase or multi-phase copolymers A.
  • the copolymer A shows very good miscibility with polyurethane finishing agent, without the need to have crosslinkable groups with polyurethanes.
  • the copolymer A can show the advantages according to the invention in combination with polyurethanes without the need to use crosslinking agents for the two components.
  • the dispersed copolymers A used according to the invention are filmable when applied to a glass plate and preferably form a hard film. In combination with polyurethanes, this results in medium-hard and hard phases.
  • the finishing agents according to the invention can contain 0 to 15% by weight of a polyurethane crosslinking agent D based on polyfunctional isocyanates, e.g. based on hexamethylene-1,6-diisocyanate with up to about 15% reactive isocyanate groups and / or 0 to 15% by weight of an aziridine crosslinker E of the trimethylolpropane tris (beta-aziridino) propionate type.
  • the finishing agent can also be free from these crosslinkers.
  • copolymers A used in the finishing agents according to the invention meet the quality requirements for a top coat in an outstanding manner, although cast films are brittle and have little or no elasticity.
  • the invention also relates to the use of the copolymers A described above as a finish or top coat for leather.
  • the invention relates to the use of the finishing agents described for surface treatment of leather.
  • the finishing agents can be prepared according to the invention, for example, by emulsion or step polymerization of the monomers AI, A2 and optionally A3 to give an aqueous dispersion of the copolymer A, and if appropriate mixing with the polyurethane finishing agent C.
  • the polyurethane finishing agent is a polyurethane in the form of an aqueous dispersion , as it has been used in leather finishing for several years now, e.g. the dispersion of a reaction product from polyester polyol [reaction product from aliphatic alcohols, e.g. Neopentyl glycol and 1,6-hexanediol, and aliphatic dicarboxylic acids, e.g. adipic acid] with dimethylolpropionic acid / triethylamine, diethylene triamine and isophorone diisocyanate.
  • polyester polyol reaction product from aliphatic alcohols, e.g. Neopentyl glycol and
  • An opacifying agent eg Aerosil ® TS 100
  • Aerosil ® TS 100 can also be added for matting effects.
  • finishing agent according to the invention it is possible to meet the requirements for clothing and shoe upper leather.
  • crosslinking agents all the required fastness properties are achieved with and without the use of polyurethane topcoat components. A good level of authenticity is also predominantly achieved when used without a crosslinker.
  • an inexpensive finishing agent can be provided that meets the requirements set out at the beginning. It can completely or partially replace the known finishing agents, especially those based on polyurethane.
  • a dispersion with a solids content of about 40% is obtained.
  • the resulting film is free of specks and hard and brittle after drying completely.
  • a glass transition temperature between 45 ° C and 50 ° C is determined.
  • the size of the dispersion particles is less than 200 nm.
  • the viscosity of the dispersion has a value between 20 and 100 mPa.s, measured according to Brookfield.
  • a dispersion with a solids content of about 40% is obtained.
  • the resulting film is free of specks and hard and brittle after complete drying, a glass transition temperature of 34 ° C is determined, a second glass transition stage in the range of 100 ° C is only indicated in the DSC measurement.
  • the size of the dispersion particles is less than 200 nm.
  • the viscosity of the dispersion has a value between 20 and 100 mPa.s, measured according to Brookfield.
  • a dispersion with a solids content of about 40% is obtained.
  • the resulting film is free of specks and hard and brittle after complete drying, a glass transition temperature of 25 ° C is determined, a second glass transition stage in the A range of 100 ° C is indicated in the DSC measurement.
  • the size of the dispersion particles is below 100 nm.
  • the viscosity of the dispersion has a value between 30 and 100 mPa.s, measured according to Brookfield.
  • a dispersion with a solids content of about 40% is obtained.
  • the resulting film is free of specks and hard and brittle after complete drying.
  • a glass transition temperature of 27 ° C is determined, a second glass transition stage in the range of 100 ° C is indicated in the DSC measurement.
  • the size of the dispersion particles is less than 150 nm.
  • the viscosity of the dispersion has a value between 50 and 150 mPa.s, measured according to Brookfield.
  • feed la 500.0 parts by weight Demineralized water 2.4 parts by weight Na-pyrophosphate
  • a dispersion with a solids content of about 40% is obtained.
  • the resulting film is free of specks and hard and brittle after complete drying, a glass transition temperature of 28 ° C is determined, and a second glass transition stage at 112 ° C.
  • the size of the dispersion particles is less than 180 nm.
  • the viscosity of the dispersion has a value less than 100 mPa.s, measured according to Brookfield.
  • Examples 5a, 5b, 5c are dispersions which were prepared analogously to Example 5 (i.e. the same additives, the same polymerization times). Only the monomer combination in the feeds la (called stage 1) and lb (called stage 2) was changed: 5a) stage 1 corresponds to the composition: 20% n-BA / 20% EA / 33.5% t-BMA
  • Level 2 corresponds to the composition: 24% t-BMA, 0.75 AS
  • Level 1 corresponds to the composition: 20% n-BA / 15% EA / 38.5% MMA / 1% AM / 0.75 AS
  • Level 2 corresponds to the composition: 24% MMA / 0.75 AS
  • Level 1 corresponds to the composition: 20% n-BA / 15% EA / 38.5% MMA / 1% AM / 0.75
  • Level 2 corresponds to the composition: 16% t-BMA / 8% n- BMA / 0.75%
  • Examples 5a to 5c give brittle films on drying with a clearly visible glass transition level between 25 and 35 ° C and a second, mostly only indicated level between 80 and 120 ° C. Sum of levels 1 and 2 100% each
  • n-BA n-butyl acrylate
  • EA ethyl acrylate
  • MMA methyl methacrylate
  • AM acrylamide
  • AS acrylic acid
  • t-BMA tertiary butyl methacrylate
  • a dispersion with a solids content of about 40% is obtained.
  • the resulting film is free of specks and hard and brittle after drying completely.
  • a glass transition temperature of 31 ° C is determined, a second glass transition stage cannot be seen.
  • the size of the dispersion particles is less than 180 nm.
  • the viscosity of the dispersion has a value less than 100 mPa.s, measured according to Brookfield.
  • Binder 50%
  • 500 wt - parts of water with 30 wt - parts of isocyanate crosslinker organic solution of a modified aliphatic polyisocyanate; commercial product BASF:... Astacin ® hardener CN in 30% Solvent
  • isocyanate crosslinker organic solution of a modified aliphatic polyisocyanate; commercial product BASF:... Astacin ® hardener CN in 30% Solvent
  • a thickener for example Lepton Paste VL 1: 1 in butyl glycol
  • the commercial product Lepton ® Paste VL from BASF AG is a polyurethane in water / solvent, as is usually used as a viscosity regulator for dressing systems in the leather industry.
  • the viscosity of the aqueous finish should be 24 seconds.
  • the basic material to be protected was usually the surface of a cowhide crust onto which a colored primer was applied by means of two roll coats (20 grid).
  • Primer formulation consisting of 150 parts by weight of Lepton Black N (this commercial product from BASF AG is a fine-particle, aqueous pigment preparation with an anionic charge; with a small amount of protective colloids; free from casein and other film-forming binders), 125 parts by weight of Lepton ® Filier CEN (commercial product Lepton Filier CEN from BASF AG is a filler and anti-adhesive for priming soft, natural leather.
  • Lepton Filier CEN commercial product Lepton Filier CEN from BASF AG is a filler and anti-adhesive for priming soft, natural leather.
  • Eukesol oil base BASF AG cationic oil emulsion with 45% water content as a primer for leather
  • 50 parts by weight of water 200 parts by weight of a soft, opaque acrylate binder, 100 parts by weight of a soft, well-penetrating acrylate binder, 20 parts by weight
  • Amollan ® VC commercial product BASF AG, highly effective leveling agent for processing viscous dressing batches on the printing press in the same area uf. Use in combination with Amollan ® E from BASF AG), 10 parts by weight of Amollan E, and x parts by weight of the thickener already described to set a viscosity of about 60 "in the Ford cup nozzle 6.
  • a typical elegant, slightly matt finish formulation with a pleasant feel for upper leather consists of 150 parts by weight of acrylate / methacrylate binder (40%), 150 parts by weight of matting agent (30%, aliphatic polyester urethane with a inorganic matting agents; Commercial product BASF: Astacin ® Mattêt MA), 50 parts by weight of wax emulsion (12% aqueous wax dispersion as filler and handle; commercial product BASF: Lepton ® Filier H) without or with up to 30 parts by weight of isocyanate
  • Crosslinker organic solution of a modified aliphatic polyisocyanate; commercial product BASF: Astacin hardener CN in 30% solvent
  • Lepton Paste VL is a polyurethane in water / solvent, as is usually used as a viscosity regulator for dressing systems in the leather industry.
  • the viscosity of the aqueous finish should be 24 seconds.
  • the application is achieved with two syringes. Further operations: ironing 120 ° C / 20 bar, milling, ironing 120 ° C / 10 bar.
  • the finish is z. B. sprayed onto a primer of the following composition:
  • Lepton Black N finely divided, aqueous pigment preparation with anionic charge; with a small amount of protective colloids; free from casein and other film-forming binders
  • Eukesol oil base cationic oil emulsion with 45% water content as Primer for leather
  • wax emulsion 12% aqueous wax dispersion as filler and handle; commercial product BASF: Lepton ® Filier H
  • 450 parts by weight of water 70 parts by weight of a 20% aqueous polyurethane dispersion; which improves the adhesive strength of the application layers even on hydrophobic or greasy surfaces without impairing the hydrophobicity (Astacin ® Grund UH from BASF AG)
  • 80 parts by weight of a soft, cold-flexible acrylate binder 150 parts by weight of a soft, well-covering acrylate binder, spray application by 3x.
  • Example B Finishing according to Example B, upper leather, with 150 parts by weight of acrylate / methacrylate binder according to Examples 2, 3 and 4.
  • Example C clothing leather, with 200 parts by weight of acrylate / methacrylate binder in accordance with Examples 5a to 5c.
  • Example 5 The dispersion according to Example 5 was tested in test recipe A for furniture leather and compared with two conventional nitrocellulose emulsion coatings.
  • the patterns are very similar in terms of gloss and feel. Also the
  • the dispersion according to Example 6 was compared directly with two conventional nitrocellulose emulsion coatings (same weight applied to upper leather).
  • the commercial products Corial EM Finish G and Corial ® EM Finish KN from BASF AG were used.
  • the coating with the dispersion on shoe upper leather finish consisting of 200 parts binder, 300 parts water, 30

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

L'invention concerne un agent d'apprêtage pour le cuir, contenant (a) 20 à 60 % en poids d'au moins un copolymère A en dispersion comprenant (a1) 40 à 70 % en poids d'au moins un ester A1 d'acide méthacrylique avec des alcanols C1-8, (a2) 25 à 60 % en poids d'au moins un ester A2 d'acide acrylique avec des alcanols C1-8, (a3) 0 à 3,5 % en poids d'au moins un acide carboxylique A3 à insaturation α,β monoéthylénique comportant 3 à 6 atomes de carbone, (a4) 0 à 4 % en poids d'au moins un autre monomère auxiliaire A4 tel que l'hydroxypropylacrylate, l'uréidométhacrylate, l'acrylamide, le méthacrylamide, le N-méthylol-acrylamide ou le N-méthylol-méthacrylamide, la somme de A1, A2 et éventuellement A3 et/ou A4 représentant 100 % en poids, (b) au moins 40 % en poids d'eau (B), (c) 0 à 40 % en poids d'agent d'apprêtage polyuréthanne C pour le cuir, la somme de A, B et éventuellement C représentant 100 % en poids et l'agent d'apprêtage étant exempt de plastifiants et de cires synthétiques.
PCT/EP2002/010088 2001-09-10 2002-09-09 Agent d'appretage pour le cuir WO2003023071A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10/488,106 US20040245490A1 (en) 2001-09-28 2002-09-09 Top coating composition for leather
EP02781181A EP1427863A1 (fr) 2001-09-10 2002-09-09 Agent d'appretage pour le cuir

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2001144319 DE10144319A1 (de) 2001-09-10 2001-09-10 Appreturmittel für Leder
DE10144319.6 2001-09-10

Publications (1)

Publication Number Publication Date
WO2003023071A1 true WO2003023071A1 (fr) 2003-03-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/010088 WO2003023071A1 (fr) 2001-09-10 2002-09-09 Agent d'appretage pour le cuir

Country Status (3)

Country Link
EP (1) EP1427863A1 (fr)
DE (1) DE10144319A1 (fr)
WO (1) WO2003023071A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202006011724U1 (de) * 2006-07-31 2007-12-06 Schaefer, Philipp Fahrzeugsitz
WO2010119002A1 (fr) 2009-04-16 2010-10-21 Basf Se Particules sphériques et leur utilisation
US8309647B2 (en) 2007-01-08 2012-11-13 Basf Se Spherical particles, method for production of spherical particles and use thereof
DE102013210787A1 (de) 2013-06-10 2014-12-11 Basf Se Sphärische Partikel und ihre Verwendung
EP3283569B1 (fr) 2015-04-17 2020-12-09 DSM IP Assets B.V. Dispersion aqueuse et utilisations associées

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6247492B2 (ja) 2012-11-06 2017-12-13 ダウ グローバル テクノロジーズ エルエルシー 水性皮革コーティング組成物および皮革をコーティングするための方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3119967A1 (de) * 1981-05-20 1982-12-16 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von konzentrierten polyacrylat-dispersionen
US4514184A (en) * 1982-05-03 1985-04-30 Henkel Corporation Leather treatment composition and leather treating
EP0437742A1 (fr) * 1990-01-16 1991-07-24 BASF Aktiengesellschaft Compositions de polymère aqueux

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3119967A1 (de) * 1981-05-20 1982-12-16 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von konzentrierten polyacrylat-dispersionen
US4514184A (en) * 1982-05-03 1985-04-30 Henkel Corporation Leather treatment composition and leather treating
EP0437742A1 (fr) * 1990-01-16 1991-07-24 BASF Aktiengesellschaft Compositions de polymère aqueux

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202006011724U1 (de) * 2006-07-31 2007-12-06 Schaefer, Philipp Fahrzeugsitz
US8309647B2 (en) 2007-01-08 2012-11-13 Basf Se Spherical particles, method for production of spherical particles and use thereof
WO2010119002A1 (fr) 2009-04-16 2010-10-21 Basf Se Particules sphériques et leur utilisation
DE102013210787A1 (de) 2013-06-10 2014-12-11 Basf Se Sphärische Partikel und ihre Verwendung
EP3283569B1 (fr) 2015-04-17 2020-12-09 DSM IP Assets B.V. Dispersion aqueuse et utilisations associées

Also Published As

Publication number Publication date
DE10144319A1 (de) 2003-03-27
EP1427863A1 (fr) 2004-06-16

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