EP0255013A2 - Couche primaire d'adhérence pour apprêts - Google Patents

Couche primaire d'adhérence pour apprêts Download PDF

Info

Publication number
EP0255013A2
EP0255013A2 EP87110470A EP87110470A EP0255013A2 EP 0255013 A2 EP0255013 A2 EP 0255013A2 EP 87110470 A EP87110470 A EP 87110470A EP 87110470 A EP87110470 A EP 87110470A EP 0255013 A2 EP0255013 A2 EP 0255013A2
Authority
EP
European Patent Office
Prior art keywords
weight
greased
ether phosphates
parts
primer
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.)
Withdrawn
Application number
EP87110470A
Other languages
German (de)
English (en)
Other versions
EP0255013A3 (fr
Inventor
Hermann Dr. Anzinger
Hans-Herbert Dr. Friese
Gerhard Kaindl
Michael Dr. Marschner
Uwe Dr. Ploog
Ludwig Dr. Schieferstein
Horst Schulz
Rolf Tenhaef
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0255013A2 publication Critical patent/EP0255013A2/fr
Publication of EP0255013A3 publication Critical patent/EP0255013A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C14SKINS; HIDES; PELTS; LEATHER
    • C14CCHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00Surface finishing of leather

Definitions

  • the invention relates to a method for improving the adhesion of dressings to greased and / or hydrophobized leathers and to the use of aqueous dispersions as a primer for improving the adhesion of dressings to greased and / or hydrophobic leathers.
  • Leather finishing is the protective layer that is applied to the leather that has been dried after tanning and greasing in order to protect it against moisture, dirt and damage.
  • An optimal dressing is required, among other things, that it adheres well to the leather.
  • most dressing systems do not meet this requirement satisfactorily: For example, very good fastness values and flexibility can be achieved with dressings based on polyurethane, so that breaking of the dressing film is almost impossible; liability problems often arise here (see "The Leather” 25 , 167-171 (1974)).
  • Another problem with hydrophobized leathers is that in many cases an improvement in the adhesion is associated with a deterioration in the hydrophobization.
  • the object of the invention was therefore to develop a primer for improving the adhesion of dressings.
  • aqueous dispersions containing A) short- and / or medium-chain alkyl ether phosphates and B) finely divided, soft, urea group-terminated, aliphatic anionic polyurethane dispersions, on greased and / or hydrophobized leathers provide a very good primer for the form subsequent dressing processes. Furthermore, it was found that the improvement in the adhesion of the finish is not associated with a negative influence on the hydrophobization in the case of leathers which have been rendered hydrophobic.
  • the alkyl ether phosphates contained in the aqueous dispersions preferably have 2 to 12 carbon atoms in the branched and / or unbranched alkyl chains and 2 to 6 alkylene oxide units in the ether chains. Alkyl ether phosphates with 2 to 6 ethylene oxide and / or propylene oxide units in the ether chains are particularly preferred.
  • alkyl ether phosphates are prepared in a manner known per se by phosphating alkoxylated, in particular ethoxylated and / or propoxylated, primary, secondary and / or tertiary, straight-chain and / or branched-chain, aliphatic alcohols having 2 to 12 carbon atoms.
  • alkyl ether phosphates means - depending on the production conditions - mono-, di- and / or trialkyl ether phosphates.
  • mono-, di- and / or trialkyl ether phosphates preferably mono- and / or dialkyl ether phosphates, are used.
  • the fine-particle, soft, urea group-terminated, aliphatic, anionic polyurethane dispersions suitable for the process according to the invention are prepared in a manner known per se (see, for example, D. Dieterich in Angew. Makrom. Chem. 98 , 133 (1981) and the literature cited therein), for example, by reacting aliphatic polyisocyanates with substoichiometric amounts of polyols in a melt reaction under an inert gas atmosphere to give the corresponding prepolymers.
  • the prepolymers are then mixed with a deficit of mono- and / or polybasic polyhydroxycarboxylic acids in the form of their alkali, amine and / or ammonium salts, dissolved in an inert solvent. After the reaction solution has been refluxed for about 1 to 3 hours, the solvent is removed in vacuo and the polyurethane composition is first dispersed in water and then in aqueous solutions containing amines and / or ammonia.
  • Suitable aliphatic polyisocyanates are, in particular, cyclic and / or non-cyclic diisocyanates, for example 1,6-hexamethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate and / or 2-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate).
  • the second component required to prepare the prepolymers, the polyols are preferably polyester and / or polyether diols known per se from polyurethane chemistry with at least 2 alcoholic hydroxyl groups and a molecular weight between about 400 and 3,000, preferably between about 800 and 2,000.
  • Difunctional polypropylene glycols are preferably used.
  • Suitable mono- and / or polybasic polyhydroxycarboxylic acids are, for example, dihydroxypropionic acid, dimethylolpropionic acid, dihydroxysuccinic acid and / or dihydroxybenzoic acid. 2,2-Dimethylolpropionic acid is preferably used.
  • Acetone and / or N-methylpyrrolidone are particularly suitable as solvents for the above-mentioned polyhydroxycarboxylic acids, which are used in the form of their alkali metal, amine and / or ammonium salts.
  • the adhesive base liquors of the process according to the invention preferably contain 2 to 20 parts by weight of water, particularly preferably 4 to 15 parts by weight of water, 1 part by weight of the polyurethane dispersion characterized above. It has been shown that, in order to improve the adhesion of dressings, there are advantages in particular in aqueous dispersions in which the weight ratio of components A: B is between about 2: 1 and about 1:10. Mixtures in which the weight ratio of components A: B is between about 1: 1 and about 1: 5 are particularly preferred.
  • the adhesive base liquors, containing components A and B, are greased using the process according to the invention and / or water-repellent leather injected or cast, preferably sprayed.
  • the alkyl ether phosphates in the aqueous dispersions to be used according to the invention preferably contain 2 to 12 carbon atoms in the branched and / or unbranched alkyl chains and 2 to 6 alkylene oxide units in the ether chains.
  • Alkyl ether phosphates which have 2 to 6 ethylene oxide and / or propylene oxide units in the ether chains are particularly preferred.
  • alkyl ether phosphates means - depending on the production conditions - mono-, di- and / or trialkyl ether phosphates.
  • the finely divided, soft, urea group-terminated, aliphatic, anionic polyurethane dispersions containing the aqueous dispersions to be used according to the invention are prepared in a manner known per se (see, for example, D. Dieterich in Angew. Makrom. Chem. 98 , 133 (1981) and the literature cited therein ) produced, for example by aliphatic polyisocyanates and substoichiometric amounts of polyols in a melt reaction under an inert gas atmosphere, the corresponding prepolymers are formed.
  • prepolymers are then mixed with a deficit of mono- and / or polybasic polyhydroxycarboxylic acids in the form of their alkali, amine and / or ammonium salts, dissolved in an inert solvent. After refluxing for about 1 to 3 hours, the solvent is removed in vacuo and the polyurethane composition is first dispersed in water and then in an aqueous solution which contains amines and / or ammonia.
  • Suitable aliphatic polyisocyanates are, in particular, cyclic and / or noncyclic diisocyanates, for example 1,6-hexamethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate and / or 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate).
  • the preferred polyols required for the preparation of the prepolymers are polyester and / or polyether diols known per se from polyurethane chemistry with at least 2 alcoholic hydroxyl groups and a molecular weight between approximately 400 and 3000, preferably between approximately 800 and 2000. Difunctional polypropylene glycols are particularly preferably used.
  • Suitable mono- and / or polybasic polyhydroxycarboxylic acids are, for example, dihydroxypropionic acid, dimethylolpropionic acid, dihydroxysuccinic acid and / or dihydroxybenzoic acid. 2,2-Dimethylolpropionic acid is preferably used.
  • Acetone and / or N-methylpyrrolidone are particularly suitable as solvents for the above-mentioned polyhydroxycarboxylic acids, which are used in the form of their alkali metal, amine and / or ammonium salts.
  • the aqueous dispersions used as a primer for dressings on greased and / or hydrophobized leathers preferably contain 1 part by weight of the polyurethane dispersion characterized above in 2 to 20 parts by weight of water, particularly preferably in 4 to 15 parts by weight of water, wherein the weight ratio of components A: B is preferably between about 2: 1 and about 1:10.
  • Aqueous dispersions in which the weight ratio of components A: B is between about 1: 1 and about 1: 5 are particularly preferably used.
  • the adhesive base liquors used are sprayed or poured, preferably sprayed, onto greased and / or hydrophobized leather.
  • the proportion of the polyurethane dispersion in the base liquor is between 1 and 50 parts by weight, preferably between 2 and 30 parts by weight, per 100 parts by weight of binder in the base liquor.
  • the weight ratio of components A: B is preferably between about 2: 1 and about 1:10, particularly preferably between about 1: 1 and about 1: 5.
  • Binder includes, for example, acrylate, acrylonitrile, polybutadiene and / or Understand polyurethane dispersions.
  • aqueous dispersions according to the invention containing A) short- and / or medium-chain alkyl ether phosphates and B) fine-particle, soft, urea-group-terminated, aliphatic, anionic polyurethane dispersions form a very good primer for greased and / or hydrophobized leathers the subsequent dressing processes.
  • the mixtures penetrate very deeply into the leather so that there are no sticking problems when ironing and stacking during the finishing processes.
  • the process according to the invention or the use according to the invention of the aqueous dispersions characterized above in the case of hydrophobized leathers creates a very good primer without negatively influencing the hydrophobization.
  • the mixture is cooled to about 70 ° C. and the reaction mixture in 59.0 parts by weight of water with very strong Dispersed stirring. Then the dispersion is mixed with 1.73 parts by weight of 12.5% NH3 / H2O solution and stirred at 50 ° C for about 1 hour.
  • the polyurethane dispersion obtained has the following characteristics: Solids content: 39% by weight pH: 7.0 Particle diameter: 58 to 80 nm Film: clear, soft, very sticky.

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)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
EP87110470A 1986-07-28 1987-07-20 Couche primaire d'adhérence pour apprêts Withdrawn EP0255013A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3625442A DE3625442C1 (de) 1986-07-28 1986-07-28 Haftgrund fuer Zurichtungen
DE3625442 1986-07-28

Publications (2)

Publication Number Publication Date
EP0255013A2 true EP0255013A2 (fr) 1988-02-03
EP0255013A3 EP0255013A3 (fr) 1989-08-09

Family

ID=6306114

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87110470A Withdrawn EP0255013A3 (fr) 1986-07-28 1987-07-20 Couche primaire d'adhérence pour apprêts

Country Status (6)

Country Link
US (1) US4772289A (fr)
EP (1) EP0255013A3 (fr)
BR (1) BR8703866A (fr)
DE (1) DE3625442C1 (fr)
IN (1) IN169304B (fr)
TR (1) TR23351A (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3922493A1 (de) * 1989-07-08 1991-01-17 Bayer Ag Verfahren zur herstellung von waessrigen dispersionen von polyurethanen und ihre verwendung als beschichtungsmittel fuer beliebige substrate
DE4003422A1 (de) * 1990-02-06 1991-08-08 Basf Ag Waessrige polyurethanzubereitungen
US5770264A (en) * 1992-07-31 1998-06-23 Bayer Aktiengesellschaft Anionically modified polyurethane ureas having reduced tackiness for the coating of leather
US6875212B2 (en) 2000-06-23 2005-04-05 Vertelink Corporation Curable media for implantable medical device
US6899713B2 (en) 2000-06-23 2005-05-31 Vertelink Corporation Formable orthopedic fixation system
CA2414168C (fr) 2000-06-23 2010-02-09 University Of Southern California Systeme de fusion vertebrale percutanee
US6964667B2 (en) 2000-06-23 2005-11-15 Sdgi Holdings, Inc. Formed in place fixation system with thermal acceleration
US7771476B2 (en) 2006-12-21 2010-08-10 Warsaw Orthopedic Inc. Curable orthopedic implant devices configured to harden after placement in vivo by application of a cure-initiating energy before insertion
US8758407B2 (en) 2006-12-21 2014-06-24 Warsaw Orthopedic, Inc. Methods for positioning a load-bearing orthopedic implant device in vivo
US8663328B2 (en) 2006-12-21 2014-03-04 Warsaw Orthopedic, Inc. Methods for positioning a load-bearing component of an orthopedic implant device by inserting a malleable device that hardens in vivo
US8480718B2 (en) 2006-12-21 2013-07-09 Warsaw Orthopedic, Inc. Curable orthopedic implant devices configured to be hardened after placement in vivo
CN110565389B (zh) * 2019-09-05 2022-02-22 兴业皮革科技股份有限公司 一种提高皮革涂层耐水洗、耐寒曲折的涂饰方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1028208A (fr) * 1973-10-05 1978-03-21 Basf Aktiengesellschaft Moyens d'enregistrement magnetique enduits
FR2247484B1 (fr) * 1973-10-12 1978-05-26 Rhone Progil
US4018559A (en) * 1974-06-14 1977-04-19 Diamond Shamrock Corporation Non-rewet leather and method of producing same
US3941733A (en) * 1975-01-02 1976-03-02 Minnesota Mining And Manufacturing Company Silanol-containing urethane dispersions

Also Published As

Publication number Publication date
IN169304B (fr) 1991-09-28
EP0255013A3 (fr) 1989-08-09
DE3625442C1 (de) 1987-11-05
US4772289A (en) 1988-09-20
TR23351A (tr) 1989-12-19
BR8703866A (pt) 1988-03-29

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Inventor name: MARSCHNER, MICHAEL, DR.

Inventor name: SCHULZ, HORST

Inventor name: FRIESE, HANS-HERBERT, DR.

Inventor name: SCHIEFERSTEIN, LUDWIG, DR.

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Inventor name: KAINDL, GERHARD