EP0204162B1 - Procédé de graissage de cuir et son application à l'aspersion directe de polyuréthane en vue de la liaison cuir/polyuréthane - Google Patents

Procédé de graissage de cuir et son application à l'aspersion directe de polyuréthane en vue de la liaison cuir/polyuréthane Download PDF

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Publication number
EP0204162B1
EP0204162B1 EP86106114A EP86106114A EP0204162B1 EP 0204162 B1 EP0204162 B1 EP 0204162B1 EP 86106114 A EP86106114 A EP 86106114A EP 86106114 A EP86106114 A EP 86106114A EP 0204162 B1 EP0204162 B1 EP 0204162B1
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EP
European Patent Office
Prior art keywords
leather
fat
liquoring
molecular weight
contain
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 - Lifetime
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EP86106114A
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German (de)
English (en)
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EP0204162A3 (en
EP0204162A2 (fr
Inventor
Harro Dr. Träubel
Helmut Dr. Woynar
Hans-Werner Müller
Hans Jürgen Focks
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Bayer AG
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Bayer AG
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Publication date
Application filed by Bayer AG filed Critical Bayer AG
Priority to AT86106114T priority Critical patent/ATE51031T1/de
Publication of EP0204162A2 publication Critical patent/EP0204162A2/fr
Publication of EP0204162A3 publication Critical patent/EP0204162A3/de
Application granted granted Critical
Publication of EP0204162B1 publication Critical patent/EP0204162B1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with 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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

Definitions

  • FR-A-1 573 918 describes a process for treating leather with aqueous emulsions of certain polyoxyalkylene glycols, e.g. Polyoxyethylene glycol, polyoxypropylene glycol, known.
  • This process can be carried out economically if the leather used is finished with products which have good adhesion under the processing conditions with polyurethanes, as is the case, for example, with with PU-coated split leather.
  • this direct injection creates problems when the leather is to be processed naturally, because the products necessary for the usual greasing of the leather usually only appear superficially and thus act as a separating agent between leather and PUR material.
  • a high level of adhesion, as required in particular for sports shoes, cannot be achieved because the polyurethane cannot bond sufficiently to the greasing material that has diffused to the surface of the leather and therefore not to the leather itself under the heat generated during the injection process .
  • the Mannich bases based on nonylphenol, or their alkoxylation products (according to US Pat. No. 3,720,606), which can in principle be used in the same way, have a catalytic effect on other isocyanate reactions, for example on the NCO-OH reactions or the NCO trimerization, and improve the adhesion not either.
  • Polyglycol etheramines behave similarly in accordance with DE-OS 2 539 671).
  • leather which adheres well to polyurethanes and is suitable for the direct injection of PUR reactive compositions is obtained if the leather, optionally after customary retanning, together with or instead of the normal leather greasing agent with at least 2, preferably aliphatic or cycloaliphatic, bonded hydroxyl groups containing polyesters and polyethers, the molecular weights of which are between 200 and 20,000, preferably 400 to 10,000, and which are transferable into the aqueous phase as such or, if appropriate, using emulsifiers and / or water-miscible solubilizers. It has also been found that leather treated in this way surprisingly has an excellent depth of color and levelness when dyed with conventional leather dyes. Color depth and levelness is much cheaper than when treating leather with common greasing agents.
  • the compounds to be used according to the invention if they are not inherently water-soluble, can also be transferred into the aqueous phase by using a suitable emulsifier as a dispersion or emulsion or by using a water-miscible solvent as solubilizer.
  • Oxiranes such as ethylene oxide, 1,2-propylene oxide, 2,3-butylene oxide, 1,2-butylene oxide, epichlorohydrin or styrene oxide, oxetanes such as 1,3-propylene oxide and oxolanes such as tetrahydrofuran are suitable for the preparation of the hydroxypolyethers. These are generally reacted with di- or polyvalent, hydroxyl- and / or amino-functional starting components to give the polyethers a) by processes which are well known per se.
  • the polyethers should contain more than 3 oxyalkylene groups.
  • Hydroxyl functional initiators such as water, diols, e.g. Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-, 3,6-dianhydrosorbitol, 4,4'-dihydroxydiphenylpropane, triols such as glycerol, trimethylolpropane, higher polyols such as pentaerythritol, sorbitol, mannitol, formite, formose or sucrose, furthermore amino-functional starters such as methylamine, ethylenediamine or stearylamine, and other starters, for example Hydrazine, oxethyl methylamine, which result in at least bifunctional polyethers.
  • diols e.g. Ethylene glycol, 1,2-propanediol, 1,3-propaned
  • Polymerization products of ethylene oxide and propylene oxide based on starting components with two or three hydroxyl groups are preferred.
  • the ratio of ethylene oxide to propylene oxide should particularly preferably be 100: 1 to 30:70, preferably 80:20 to 40:60. It was surprising that polyethers based on hydroxy-functional starters produce fatliquoring agents which result in significantly improved coloring and color levelness with high dyeing fastness to rubbing.
  • amino-functional hydroxypolyethers often give rise to complexes with acid dyes, which are deposited on the leather surface (in the form of color salts) and give low-abrasion-resistant dyeings.
  • acidification of the dyed leather is difficult (poor bath consumption) and the fixing of the dyes on the leather surface is sometimes difficult.
  • polyether polyols that have started on longer-chain amines (e.g. with & 10 C atoms)
  • a lot of foam occurs during the coloring (due to the side effect), which ultimately results in uneven coloring.
  • the suitable hydroxypolyesters to be used according to the invention can be prepared in a manner known per se and are e.g. Reaction products of polyvalent, preferably dibasic carboxylic acids or their mixtures.
  • the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower, monohydric alcohols or mixtures thereof can also be used to produce the polyesters.
  • the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic, araliphatic and / or heterocyclic in nature and optionally substituted, e.g. by halogen atoms such as chlorine or bromine and / or unsaturated.
  • carboxylic acids and their derivatives are: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, indomethylene tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimerized and trimerized unsaturated fatty acid, such as a mixture of fatty acids, unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids and unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as a mixture of unsaturated fatty acids, such as
  • polyhydric alcohols optionally in a mixture with one another, for example Ethylene glycol, 1,2-and 1,3-propanediol, 1,4-butanediol and 2,3-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2-methyl-1,3 -propanediol, N, N-bis- (2-hydroxypropyl) -N-methylamine, glycerin, trimethylolpropane, hexanetriol-1,2,6, butanetriol-1,2,4, trimethylolethane, pentaerythritol, quinite, mannitol, sorbitol, formitol , Methylglycoside, dianhydrohexite, ° furthermore in particular di-, tri-, tetra-ethylene glycols and higher polyethylene glycols, furthermore di-
  • the low molecular weight polyols can also be set in any mixtures by esterification.
  • the polyesters to be used can also have a proportion of carboxyl groups as end groups.
  • Lactone polyesters e.g. Caprolactone or hydroxycarboxylic acids, e.g. e-Hydroxycaproic acid, these compounds being used either alone or as a mixture with polyhydroxyl compounds to prepare the polyesters.
  • Preferred polyesters are hydrophilic polyesters or else hydrophilic polycarbonates which have been produced using di-, tri-, tetra- or polyethylene glycols.
  • the polycarbonates which can also be used can be prepared in a manner known per se and are e.g. Reaction products of polyhydric, preferably two and optionally three or tetravalent alcohols, with certain carbonic acid derivatives such as phosgene, phenyl chloroformate, ethyl chloroformate, but especially diphenyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate or dimethyl pyrocarbonate.
  • polyhydric preferably two and optionally three or tetravalent alcohols
  • certain carbonic acid derivatives such as phosgene, phenyl chloroformate, ethyl chloroformate, but especially diphenyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate or dimethyl pyrocarbonate.
  • polyesters, polylactones and / or polycarbonates can also be used. Unless they are inherently soluble, emulsifiable or dispersible in water, the polyethers, polyesters or polycarbonates according to the invention can be transferred into the aqueous phase by adding conventional emulsifiers.
  • the emulsifiability of polyesters, polylactones, polycarbonates or polyethers is also simplified by incorporating small amounts of ionizable groups (cationic or anionic type or of tertiary amines which can form salts).
  • Possible external emulsifiers are: long-chain alkyl sulfates or alkyl sulfonates, ethoxylation products of alkylphenols, e.g. para-nonylphenol or of aromatically substituted phenols such as phenylphenol or of alkylation or benzylation products of phenylphenol; long chain alkyl carboxylic acids or quaternized long chain alkyl ammonium salts.
  • the products which can be used according to the invention are used together with or instead of the normal leather greasing agents.
  • the amount of normal leather greasing agents known per se is generally restricted to amounts of less than 80% by weight.
  • leather greasing is used to impart the final softness to the leather before and especially after dyeing.
  • the fatliquors so superficially that later operations such as dressing or, in particular, the direct injection of polyurethane soles are severely hampered by the fatliquors which act as release agents in this case.
  • the products to be used according to the invention do not show these disadvantages. Their use thus represents a significant improvement in the further processing of the leather treated with them.
  • the leather treated according to the invention can be dyed excellently with deep shades with high levelness.
  • the leathers are subjected to the usual post-treatment, e.g. dried, pounded and optionally prepared by known methods.
  • the polyurethane reactive compositions are now sprayed directly onto the leather which has been greased in accordance with the invention and has been prepared in this way. It has also been shown that - depending on the plasticizers used - these leathers are also well suited for the injection of PVC or using classic methods, e.g. after preparation, can be processed.
  • hydroxyl-polycarbonate greasing agents in particular hydroxy-polyalkylene oxide polycarbonates as greasing agents.
  • the fatliquoring agents a) to d) according to the invention are generally used in the field of leather production which is carried out with "wet finishing". is marked, ie in the area of retanning / greasing. Exemplary applications can be found in the description in the examples.
  • results that can be achieved by the process according to the invention or the use according to the invention depend on the type of leather and on the type of tanning, as well as the type of fatliquor and the polyurethane reactive injection mixture.
  • Chrome-tanned leathers are e.g. washed, then neutralized (to pH 4.5 to 6.0) treated with 2 to 20% by weight of vegetable, mineral or organic synthetic retanning agents and, if appropriate, colored. Then 0.1 to 20% by weight of the products according to the invention and, if appropriate, additional commercially available fatliquoring agents are used and finished as usual.
  • the leather is processed in machines that are common in the shoe industry.
  • the uppers are made from the leather, a base (mostly made of textile) is sewn in, the uppers are pulled over a (metal) last and then the polyurethane materials (soles) are molded on in suitable machines.
  • the polyurethane reactive mixtures contain the usual starting components, for example higher molecular weight compounds with at least 2, preferably 2 to 4, end groups reactive towards NCO, such as OH, NH 2 , NHR, COOH or CONHNH 2 end groups, with a molecular weight of about 400 up to 10,000, the usual aliphatic, cycloaliphatic, aromatic or heterocyclic polyisocyanates as known in the prior art, and optionally low molecular weight chain extenders with the end groups mentioned and molecular weights from 18, 32 to 399, for example water, di-polyols or di- / di- / Polyamines or other known compounds.
  • the polyhydroxyl compounds can also be more complex natural substances such as castor oil or modified linseed oil.
  • the reactive mixtures can furthermore have the usual PU catalysts and other customary auxiliaries and additives, for example pigments, fillers, fibers, glass tube balls, blowing agents, stabilizers, dyes and the like.
  • NCO prepolymers or semi-prepolymers can also be used.
  • the NCO key figures can be varied in a customary range, for example from key figures 60 to key figure 125, preferably key figures 90 to 115.
  • the spraying process can be carried out by automatic metering and mixing of the reaction components, preferably in cycles.
  • the density of the polyurethane elastomers formed from the polyurethane reactive compositions can be 800 kg / m (cellular elastomers) up to the homogeneous density of the polyurethane elastomer composition.
  • 500 g of a hydroxy polycarbonate based on hexanediol polycarbonate of molecular weight 1800 are dispersed in 600 g water using 10 g of an emulsifier based on 3-benzyl-4-hydroxy-biphenyl polyglycol ether. An emulsion is formed.
  • 500 g of a bifunctional polydiethylene glycol adipate, molecular weight 2000, are dissolved in 100 g of diacetone alcohol and converted into an emulsion with 10 g of an emulsifier based on stearylamine + 8 moles of ethylene oxide and 500 g of water.
  • 500 g of a linear polyether based on oxyethylene / oxypropylene mixed ether with a molecular weight of 4000 and 18% by weight of terminal oxyethylene groups are dispersed in 500 g of water using 10 g of the above-described emulsifier and 100 g of ethyl glycol.
  • 200 g of the polyester as in Example 1.5 and 200 g of the polyether as in Example 1.1 are emulsified with 8 g of 3-benzyl-4-hydroxy-diphenyl-polyglycol ether as an emulsifier in water to form an emulsion containing 25% solids.
  • 200 g of a polyester as in Example 1.5 are emulsified with 200 g of a polyoxypropylene ether started on trimethylolpropane and 8 g of the emutifier mentioned in Example 1.8 to form a 22% emulsion in water.
  • a chrome-tanned leather is mixed with 200% water (45 ° C) and 0.2% 10% acetic acid and 2.5% of a highly lightfast exchange tanning agent (Tanigan-3LN @ , Bayer AG, Leverkusen) are added and let run for 30 minutes.
  • the liquor is drained, washed and again 200% water (45 ° C.) and 1.5% of a neutralizing syntan (Tanigan PC O , Bayer AG, Leverkusen) and 0.5% sodium bicarbonate are added.
  • a pH of 4.6 is established. After 45 minutes, the water is removed.
  • Comparable halves were treated on the one hand with a lubricant mixture known to be well effective according to the state of the art (Coripol-DX-902, Stockhausen, sperm oil replacement product Chromopol-UFB / W + chloroparaffin Coripol-ICA, Stockhausen, Krefeld - 8% refatting fat) , or (according to the invention) with 4% of the fat mixture from Example 1.1.
  • a lubricant mixture known to be well effective according to the state of the art (Coripol-DX-902, Stockhausen, sperm oil replacement product Chromopol-UFB / W + chloroparaffin Coripol-ICA, Stockhausen, Krefeld - 8% refatting fat) , or (according to the invention) with 4% of the fat mixture from Example 1.1.
  • the leather was molded directly without roughening.
  • the separating force of the PU sole mixture on the leather was determined on a tearing machine in accordance with DIN 53 328.
  • the leather can be dyed with leather dyes.
  • a very full or full coloration of the leather is achieved with the leathers greased according to the invention (greasing 2 or 3), with good to very good levelness of the coloring.
  • the color depth that can be achieved on the comparison leather with bold 1 is only slight (light) with only a moderate level.
  • the leather with grease 1, 2 and 3 was sprayed with reactive PU mixtures on a conventional automatic spray gun.
  • the results of the gating tests were:
  • the separating forces between the molded-on sole and greased leather show significantly higher values, in particular if products made from ether or ester base are used both for leather greasing and for the reactive PU composition.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (7)

1. Utilisation de cuir prétraité par des agents d'engraissement pour la pulvérisation directe de matières réactives de polyuréthannes pour donner des composites cuir-polyuréthanne ayant une résistance élevée à la séparation, caractérisé en ce que l'on effectue le traitement d'engraissement du cuir tanné avec des bains aqueux d'agents d'engraissement qui contiennent, sous forme d'une solution, émulsion ou dispersion aqueuse contenant éventuellement des solvants:
a) des hydroxypolyéthers ayant au moins deux groupes hydroxyles, d'un poids moléculaire de 200 à 20 000 et/ou
b) des hydroxypolyesters ayant au moins deux groupes hydroxyles, d'un poids moléculaire de 200 à 20 000 et/ou
c) des hydroxypolycarbonates ayant au moins deux groupes hydroxyles, d'un poids moléculaire de 200 à 20 000, ou bien
d) des mélanges de composants des catégories a), b) ou c) à la place d'agents habituels d'engraissement, mais aussi en combinaison avec des agents habituels d'engraissement, jusqu'à l'absorption de 0,1 à 20% en poids des produits d'agents d'engraissement, par rapport au poids du cuir dérayé.
2. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise les cuirs prétraités sous forme de tiges avec des matières réactives de polyuréthannes dans des machines automatiques de pulvérisation avec formation de semelles composites cuir pour tige-polyuréthanne.
3. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise pour le traitement des cuirs des agents d'engraissement à base d'hydroxypolyesters et/ou d'hydroxypolycarbonates et on utilise les masses réactives de polyuréthannes à base de polyesters ou de polycarbonates pour la pulvérisation.
4. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise pour le traitement des cuirs des agents d'engraissement à base d'hydroxypolyéthers et on utilise les masses réactives de polyuréthannes à base de polyéthers pour la pulvérisation.
5. Procédé pour le traitement d'engraissement du cuir, caractérisé en ce que l'on traite les cuirs tannés par des bains aqueux d'agents d'engraissement qui contiennent, sous forme d'une solution, émulsion ou dispersion aqueuse contenant éventuellement des solvants:
a) des hydroxypolyesters ayant au moins deux groupes hydroxyles, d'un poids moléculaire de 200 à 20 000, et/ou
b) des polycarbonates ayant au moins deux groupes hydroxyles, d'un poids moléculaire de 200 à 20 000, ou bien
c) des mélanges de composants des catégories a) ou b) à la place d'agents habituels d'engraissement ou en combinaison avec des agents habituels d'engraissement, jusqu'à l'absorption de 0,1 à 20% en poids des produits d'agents d'engraissement, par rapport au poids du cuir dérayé.
6. Procédé selon la revendication 5, caractérisé en ce que les hydroxypolyesters ou hydroxypolycarbonates sont à base de di-, tri-, tétra- ou polyéthylèneglycols.
7. Procédé selon la revendication 5, caractérisé en ce que les hydroxypolyesters et/ou hydroxypolycarbonates ont un poids moléculaire de 400 à 10 000.
EP86106114A 1985-05-17 1986-05-05 Procédé de graissage de cuir et son application à l'aspersion directe de polyuréthane en vue de la liaison cuir/polyuréthane Expired - Lifetime EP0204162B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86106114T ATE51031T1 (de) 1985-05-17 1986-05-05 Verfahren zur fettungsbehandlung von leder und seine verwendung zum direkt-anspritzen von polyurethan zu leder/polyurethan-verbunden.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3517803 1985-05-17
DE19853517803 DE3517803A1 (de) 1985-05-17 1985-05-17 Verfahren zur fettungsbehandlung von leder und seine verwendung zum direkt-anspritzen von polyurethan zu leder/polyurethan-verbunden

Publications (3)

Publication Number Publication Date
EP0204162A2 EP0204162A2 (fr) 1986-12-10
EP0204162A3 EP0204162A3 (en) 1987-10-28
EP0204162B1 true EP0204162B1 (fr) 1990-03-14

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP86106114A Expired - Lifetime EP0204162B1 (fr) 1985-05-17 1986-05-05 Procédé de graissage de cuir et son application à l'aspersion directe de polyuréthane en vue de la liaison cuir/polyuréthane

Country Status (6)

Country Link
US (1) US4810251A (fr)
EP (1) EP0204162B1 (fr)
JP (1) JPH0631440B2 (fr)
AT (1) ATE51031T1 (fr)
CA (1) CA1257453A (fr)
DE (2) DE3517803A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5061517A (en) * 1989-11-22 1991-10-29 Speer Lawrence L Brush-on finish for footwear and similar articles
US5284568A (en) * 1992-07-17 1994-02-08 E. I. Du Pont De Nemours And Company Disposable cartridge for ion selective electrode sensors
US5503754A (en) * 1993-11-10 1996-04-02 Henkel Corporation Wet treatment of leather hides
DE19707713A1 (de) * 1997-02-26 1998-08-27 Basf Ag Zusammensetzung zur Behandlung von gegerbtem Leder, sowie ihre Herstellung

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2317318A1 (fr) * 1975-06-25 1977-02-04 Bayer Ag Procede de preparation de composes polyhydroxyles dispersibles dans l'eau
DE3048159A1 (de) * 1979-12-21 1981-09-03 Toyo Boseki K.K., Osaka Waessrige polyesterharzdispersion
NL8304021A (nl) * 1983-11-23 1984-12-03 Akzo Nv Stabiele waterige dispersie van een polymeer alsmede de bereiding en toepassing van een dergelijke dispersie.

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2828220A (en) * 1955-03-21 1958-03-25 Rohm & Haas Method of coating leather with polymers containing hydroxyl groups and the resulting article
FR1573918A (fr) * 1968-01-29 1969-07-11
US3720606A (en) * 1971-02-18 1973-03-13 Biogenics Co Inc Deodorizing and sewage treatment formulation
US4190687A (en) * 1972-05-09 1980-02-26 Sumitomo Chemical Company, Limited Method for treating leather
DE2231162A1 (de) * 1972-06-26 1974-01-17 Henkel & Cie Gmbh Verfahren zur herstellung kaeltebestaendiger ester hoeherer fluessiger fettsaeuren mit mehrwertigen alkoholen
CH599391A5 (fr) * 1974-09-10 1978-05-31 Sandoz Ag
DE3031187A1 (de) * 1980-08-18 1982-04-08 Röhm GmbH, 6100 Darmstadt Behandlung von leder mit hydrophilen acrylatharzen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2317318A1 (fr) * 1975-06-25 1977-02-04 Bayer Ag Procede de preparation de composes polyhydroxyles dispersibles dans l'eau
DE3048159A1 (de) * 1979-12-21 1981-09-03 Toyo Boseki K.K., Osaka Waessrige polyesterharzdispersion
NL8304021A (nl) * 1983-11-23 1984-12-03 Akzo Nv Stabiele waterige dispersie van een polymeer alsmede de bereiding en toepassing van een dergelijke dispersie.

Also Published As

Publication number Publication date
EP0204162A3 (en) 1987-10-28
CA1257453A (fr) 1989-07-18
JPS61266500A (ja) 1986-11-26
DE3669532D1 (de) 1990-04-19
DE3517803A1 (de) 1986-11-20
US4810251A (en) 1989-03-07
EP0204162A2 (fr) 1986-12-10
ATE51031T1 (de) 1990-03-15
JPH0631440B2 (ja) 1994-04-27

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