CA1143612A - Method of producing an adhesive elastomeric film - Google Patents
Method of producing an adhesive elastomeric filmInfo
- Publication number
- CA1143612A CA1143612A CA000358139A CA358139A CA1143612A CA 1143612 A CA1143612 A CA 1143612A CA 000358139 A CA000358139 A CA 000358139A CA 358139 A CA358139 A CA 358139A CA 1143612 A CA1143612 A CA 1143612A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- film
- rubber
- elastomeric film
- moulded
- 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
Links
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/48—Polyethers
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
ABSTRACT
Adhesive polyurethane or polyurea elastomeric film is produced on rubber articles by applying to the surface of the rubber article a prepolymer with reactive isocyanate end-groups and a polyaddition catalyst and chain-lengthening the prepolymer into an elastomeric film by the use of moisture.
Improved film adhesion is obtained without loss of ductility.
Adhesive polyurethane or polyurea elastomeric film is produced on rubber articles by applying to the surface of the rubber article a prepolymer with reactive isocyanate end-groups and a polyaddition catalyst and chain-lengthening the prepolymer into an elastomeric film by the use of moisture.
Improved film adhesion is obtained without loss of ductility.
Description
~3~
The invention relates to a method of producing an adhesive poly-urethane or polyurea elastomeric film upon moulded unvulcanized rubber (caout-chouc) or vulcanized synthetic or natural rubber articles.
An elastomeric film of this kind may be used either as a lacquer coating or as an adhesive for Elocking, as usually applied to moulded articles made of rubber, Eor example rubber pro11es.
In the case of elastomeric films of this kind, polymers, for example polyurethanes or polypropylenes, are applied, in the presence of aids such as polyfunctional adhesive isocyanates, polymer "blends", reactive diluents or anti-oxidants, to the surface of the moulded caoutchouc or rubber article, followed by flocking. After the solvent has been evaporated off, an adhesive, if necessary flocked, polymer-film is obtained on the surface of the moulded article, for example a profile or strip.
The disadvantage of this known process is that, during the coating operation, the solvent vapours may pollute the environment in a manner detri-mental to health. Furthermore, in the case of only slightly polar caoutchouc and rubber types, for example EPDM, the base material must be roughened be-fore the polymer is applied, in order to obtain adequate adhesion of the polymer film. This roughening of the moulded article is, however, very awk-ward and tedious, and reliably reproducible results can therefore be obtainedonly with expensive equipment and techniques.
Attempts have therefore been made to apply elastom0ric films of this kind, without using solvents and without prior roughening of the moulded article, by increasing the chemical affinity between the moulded article and the polymer material. To this end, use is made, for example, of telechelics as functional polymers in building the polyurethane-polymer film, or special adhesive isocyanates are added, for example isocyanatophenyl-sulphene chloride ~: i~
;12 or 4,4'94"-triiso-cyanato-triphenyl-methane. Even then, adhesion to slightly polar rubber types is not very satisfactory, since polymer films thus obtained tend to detach from the surfaces of moulded articles, especially under hydroly-tic conditions. In addition to this, when adhesive isocyanates are used in polymer films in concentrations in excess of 3%, this is at the expense of the high ductile yield so necessary for such films in practice.
It is therefore thepurpos0 of the present invention to provide a method of producing an adhesive polyurethane or polyurea elastomeric film, upon moulded caoutchouc or rubber articles, in which the above mentioned dis-advantages are eliminated.
More particularly, the method provides reliable adhesion of thefilm, with a sufficiently high ductile yield, without the necessity of rough-ening the moulded articles.
According to the invention, there is provided a method of producing an adhesive polyurethane or polyurea elastomeric film upon moulded caoutchouc or rubber articles, wherein a prepolymer based on 4,4'-diphenylmethane di-isocyanate and a polyaddition catalyst, optionally with the usual additives, is applied to the surface of the moulded article and is hardened, character-ized in that a polypropylene oxi.de polyol or a polytetrahydrofurane polyol, having a molecular weight of from 400 to 5000 and the 4,4'-diphenylmethane diisocyanate, are applied to the rubber article without solvent and are chain-lengthened into the elastomeric film with the use of atmospheric humidity and/or adsorption moisture. Thus, a prepolymer is used with reactive iso-cyanate end groups.
The advantages achieved with the invention are mainly that elasto-meric films produced adhere very well to standard qualities of caoutchouc and rubber, even to EPDM and EPDM/CR blends, and also produce excellent adhesion ~.
~3t;~
on flocking, such as polyamide flocking. There is no need to roughen the mouldings; instead, the raw materials for the elastomeric film may be applied directly to freshly moulded surfaces. This good adhesion is assumed to be attributable to mutual penetration of the polymer systems during the forma-tion of the polymer-polyurethane or polyurea makrix of the elastomeric film.
Use is made in the cross-linking reaction oE the water present on or in the surface of the moulded article in the form of moisture, namely adsorption moisture or atmospheric moisture, and this water can therefore no longer af-fect the adhesion of the cured polymer film on the surface of the moulding.
This function of the water may also be performed partly or wholly by a cross-linking agent on or in the moulding, for example a diol, diamine, polyol or polyamine.
An elastomeric film prepared with the same stoichiometry and chem-istry from solvents provides much poorer adhesion to rubber mouldings than an elastomeric film produced by the method according to the invention.
Particularly satisfactory adhesion is obtained if a prepolymer, optionally free of solvents, and the polyaddition catalyst, are diluted with radiation-cross-linked diluents having an acrylic-acid-derivative base, and if this material is then also cross-linked by electron-beam simultaneously with the chemical cross-linking. If the amount of electron radi~tion is correctly selected, it is possible to keep the otnerwise unavoidable decrease in ductile yield within controllable limits.
Elastomeric ~ilms of this kind may be used as adhesive films for flocked rubber profiles, for the reactive gluing of rubber with polyurethane or polyurea systems, especially for foaming and integral-foaming, and for reactive lining of polymer parts.
The inven~ion is illustrated in greater detail by the following Examples.
Example 1.
150 g of a prepolymer consisting of a polypropylene-oxide diol having an average molecular weight of 1500, and 50 g of 4,4-diphenyl-methane-diisocyanate, oblained by stirring the components for one hour at 75C, were spread, after the addition of 0.1 part by weight of dibutyl-tin-dilaurate, on a rubber article made of 2 parts by weight of EPDM and 1 part by weight of CR. Thereafter, polyamide flocking 0.6 mm in thickness was applied to this surface layer electrostatically.
Using adsorption and atmospheric-moisture, this film hardened with-in 10 minutes.
The said film was subjected to the following tests:
a) a test-piece was stored under water for 5 days at 80C. This had no effect upon the adhesion of the film or of the flocking.
b) A piece of sealing wax 1 cm in width and 9 cm in length was pressed, in a softened condition, onfo the test piece. Upon cooling, a measurement of resistance to peeling was obtained using the Daimler-Benz Test Standard (DBL 5575). The value obtained was between 2.1 and 2.5 (daN/10 mm). The standard requires a nominal value of 2.0 (daN/10 mm).
Example 2.
A prepolymer made of polytetrahydrofuran having a molecular weight of 2000 and 4,4'-diphenylmethane-diisocyanate, in a molar ratio of 1 : 2, was applied to a pure EPDM rubber by the method according to Example 1. The peeling resistance amounted to between 2.5 and 4 (daN/10 mm).
Example 3.
The prepolymer according to Example 2, but with an addition of 1%
of Desmodur R, BAYER ~G., was applied by the method according to Example 1.
The peeling resistance was between 3.0 and 3.2 (daN/10 mm). There was no ~1~3~
change in the adhesion of the film and the flocking after 5 days storage under water at 80C.
~.
Using the method described in Example 2, 5% of acrylic-acid dibutyl amide, in relation -to tlle prepolymer, was added to the filmJ and an additional cross-linking was carried out by electron-beam irradiation of 180kV electrons.
There was no change in the adhesion of the film and the flocking after 5 days storage under water at 80C.
Example 5.
A pure EPDM rubber was coated with molten 1,12-dodecamethylene-diamine, heated for a short time at 40C, and then spread at this temperature with a prepolymer according to Example 2; flocking was then applied electro-statically. The catalyst used for the prepolymer was 0.15 parts by weight of dibutyl phosphate.
The peeling resistance amounted to 2.1 (daN/10 mm).
The film did not loosen after 5 days storage under water at 80C.
Example 6.
The method according to Example 2 was used, but 0.1 parts by weight of Stabaxol 1, BAYER AG., were added to the prepolymer.
The peeling resistance amounted to between 2.5 and 4.0 ~daN/10 mm).
There was no loosening of the film or the flocking after 5 days storage in water at 80C.
The invention relates to a method of producing an adhesive poly-urethane or polyurea elastomeric film upon moulded unvulcanized rubber (caout-chouc) or vulcanized synthetic or natural rubber articles.
An elastomeric film of this kind may be used either as a lacquer coating or as an adhesive for Elocking, as usually applied to moulded articles made of rubber, Eor example rubber pro11es.
In the case of elastomeric films of this kind, polymers, for example polyurethanes or polypropylenes, are applied, in the presence of aids such as polyfunctional adhesive isocyanates, polymer "blends", reactive diluents or anti-oxidants, to the surface of the moulded caoutchouc or rubber article, followed by flocking. After the solvent has been evaporated off, an adhesive, if necessary flocked, polymer-film is obtained on the surface of the moulded article, for example a profile or strip.
The disadvantage of this known process is that, during the coating operation, the solvent vapours may pollute the environment in a manner detri-mental to health. Furthermore, in the case of only slightly polar caoutchouc and rubber types, for example EPDM, the base material must be roughened be-fore the polymer is applied, in order to obtain adequate adhesion of the polymer film. This roughening of the moulded article is, however, very awk-ward and tedious, and reliably reproducible results can therefore be obtainedonly with expensive equipment and techniques.
Attempts have therefore been made to apply elastom0ric films of this kind, without using solvents and without prior roughening of the moulded article, by increasing the chemical affinity between the moulded article and the polymer material. To this end, use is made, for example, of telechelics as functional polymers in building the polyurethane-polymer film, or special adhesive isocyanates are added, for example isocyanatophenyl-sulphene chloride ~: i~
;12 or 4,4'94"-triiso-cyanato-triphenyl-methane. Even then, adhesion to slightly polar rubber types is not very satisfactory, since polymer films thus obtained tend to detach from the surfaces of moulded articles, especially under hydroly-tic conditions. In addition to this, when adhesive isocyanates are used in polymer films in concentrations in excess of 3%, this is at the expense of the high ductile yield so necessary for such films in practice.
It is therefore thepurpos0 of the present invention to provide a method of producing an adhesive polyurethane or polyurea elastomeric film, upon moulded caoutchouc or rubber articles, in which the above mentioned dis-advantages are eliminated.
More particularly, the method provides reliable adhesion of thefilm, with a sufficiently high ductile yield, without the necessity of rough-ening the moulded articles.
According to the invention, there is provided a method of producing an adhesive polyurethane or polyurea elastomeric film upon moulded caoutchouc or rubber articles, wherein a prepolymer based on 4,4'-diphenylmethane di-isocyanate and a polyaddition catalyst, optionally with the usual additives, is applied to the surface of the moulded article and is hardened, character-ized in that a polypropylene oxi.de polyol or a polytetrahydrofurane polyol, having a molecular weight of from 400 to 5000 and the 4,4'-diphenylmethane diisocyanate, are applied to the rubber article without solvent and are chain-lengthened into the elastomeric film with the use of atmospheric humidity and/or adsorption moisture. Thus, a prepolymer is used with reactive iso-cyanate end groups.
The advantages achieved with the invention are mainly that elasto-meric films produced adhere very well to standard qualities of caoutchouc and rubber, even to EPDM and EPDM/CR blends, and also produce excellent adhesion ~.
~3t;~
on flocking, such as polyamide flocking. There is no need to roughen the mouldings; instead, the raw materials for the elastomeric film may be applied directly to freshly moulded surfaces. This good adhesion is assumed to be attributable to mutual penetration of the polymer systems during the forma-tion of the polymer-polyurethane or polyurea makrix of the elastomeric film.
Use is made in the cross-linking reaction oE the water present on or in the surface of the moulded article in the form of moisture, namely adsorption moisture or atmospheric moisture, and this water can therefore no longer af-fect the adhesion of the cured polymer film on the surface of the moulding.
This function of the water may also be performed partly or wholly by a cross-linking agent on or in the moulding, for example a diol, diamine, polyol or polyamine.
An elastomeric film prepared with the same stoichiometry and chem-istry from solvents provides much poorer adhesion to rubber mouldings than an elastomeric film produced by the method according to the invention.
Particularly satisfactory adhesion is obtained if a prepolymer, optionally free of solvents, and the polyaddition catalyst, are diluted with radiation-cross-linked diluents having an acrylic-acid-derivative base, and if this material is then also cross-linked by electron-beam simultaneously with the chemical cross-linking. If the amount of electron radi~tion is correctly selected, it is possible to keep the otnerwise unavoidable decrease in ductile yield within controllable limits.
Elastomeric ~ilms of this kind may be used as adhesive films for flocked rubber profiles, for the reactive gluing of rubber with polyurethane or polyurea systems, especially for foaming and integral-foaming, and for reactive lining of polymer parts.
The inven~ion is illustrated in greater detail by the following Examples.
Example 1.
150 g of a prepolymer consisting of a polypropylene-oxide diol having an average molecular weight of 1500, and 50 g of 4,4-diphenyl-methane-diisocyanate, oblained by stirring the components for one hour at 75C, were spread, after the addition of 0.1 part by weight of dibutyl-tin-dilaurate, on a rubber article made of 2 parts by weight of EPDM and 1 part by weight of CR. Thereafter, polyamide flocking 0.6 mm in thickness was applied to this surface layer electrostatically.
Using adsorption and atmospheric-moisture, this film hardened with-in 10 minutes.
The said film was subjected to the following tests:
a) a test-piece was stored under water for 5 days at 80C. This had no effect upon the adhesion of the film or of the flocking.
b) A piece of sealing wax 1 cm in width and 9 cm in length was pressed, in a softened condition, onfo the test piece. Upon cooling, a measurement of resistance to peeling was obtained using the Daimler-Benz Test Standard (DBL 5575). The value obtained was between 2.1 and 2.5 (daN/10 mm). The standard requires a nominal value of 2.0 (daN/10 mm).
Example 2.
A prepolymer made of polytetrahydrofuran having a molecular weight of 2000 and 4,4'-diphenylmethane-diisocyanate, in a molar ratio of 1 : 2, was applied to a pure EPDM rubber by the method according to Example 1. The peeling resistance amounted to between 2.5 and 4 (daN/10 mm).
Example 3.
The prepolymer according to Example 2, but with an addition of 1%
of Desmodur R, BAYER ~G., was applied by the method according to Example 1.
The peeling resistance was between 3.0 and 3.2 (daN/10 mm). There was no ~1~3~
change in the adhesion of the film and the flocking after 5 days storage under water at 80C.
~.
Using the method described in Example 2, 5% of acrylic-acid dibutyl amide, in relation -to tlle prepolymer, was added to the filmJ and an additional cross-linking was carried out by electron-beam irradiation of 180kV electrons.
There was no change in the adhesion of the film and the flocking after 5 days storage under water at 80C.
Example 5.
A pure EPDM rubber was coated with molten 1,12-dodecamethylene-diamine, heated for a short time at 40C, and then spread at this temperature with a prepolymer according to Example 2; flocking was then applied electro-statically. The catalyst used for the prepolymer was 0.15 parts by weight of dibutyl phosphate.
The peeling resistance amounted to 2.1 (daN/10 mm).
The film did not loosen after 5 days storage under water at 80C.
Example 6.
The method according to Example 2 was used, but 0.1 parts by weight of Stabaxol 1, BAYER AG., were added to the prepolymer.
The peeling resistance amounted to between 2.5 and 4.0 ~daN/10 mm).
There was no loosening of the film or the flocking after 5 days storage in water at 80C.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of producing an adhesive polyurethane or polyurea elasto-meric film upon moulded caoutchouc or rubber articles, wherein a prepolymer based on 4,4'-diphenylmethane diisocyanate and a polyaddition catalyst, the usual additives, is applied to the surface of the moulded article and is hardened, characterized in that polypropylene oxide polyol or a polytetrahydrofurane polyol, having a molecular weight of from 400 to 5000 and the 4,4'-diphenylmethane diisocyanate, are applied to the rubber article without solvent and are chain-lengthened into the elastomeric film with the use of atmospheric humidity and/or adsorption moisture.
2. A method according to claim 1, wherein the polypropylene oxide or polytetrahydrofurane polyol has a molecular weight of from 100 to 4000.
3. A method according to claim 1 or 2, wherein the catalyst is a tin compound.
4. A method according to claim 1 or 2, wherein the catalyst is dibutyl-tin-dilaurate.
5. A method according to claim 1 or 2, wherein the catalyst is a cyclic lactam.
6. A method according to claim 1 or 2, wherein the catalyst is capro-lactam.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2932866.3 | 1979-08-14 | ||
| DE2932866A DE2932866C3 (en) | 1979-08-14 | 1979-08-14 | Process for the production of an adhesive polyurethane or polyurea elastomer film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1143612A true CA1143612A (en) | 1983-03-29 |
Family
ID=6078417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000358139A Expired CA1143612A (en) | 1979-08-14 | 1980-08-13 | Method of producing an adhesive elastomeric film |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0025500A1 (en) |
| JP (1) | JPS5634442A (en) |
| CA (1) | CA1143612A (en) |
| DE (1) | DE2932866C3 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4596725A (en) * | 1984-05-04 | 1986-06-24 | Henkel Kommanditgesellschaft Auf Aktien | Polyurethane insulating foam |
| US4668323A (en) * | 1984-04-17 | 1987-05-26 | Uniroyal Englebert Textilcord S.A. | Method of making flexible, fiber-covered, sheet-like textile article |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3400852A1 (en) * | 1984-01-12 | 1985-07-25 | Henkel KGaA, 4000 Düsseldorf | ADHESIVE ELASTOMER PAINT |
| JPS60186538A (en) * | 1984-03-07 | 1985-09-24 | Dai Ichi Kogyo Seiyaku Co Ltd | Primer for polyolefin |
| JPS60245645A (en) * | 1984-05-21 | 1985-12-05 | Toyoda Gosei Co Ltd | Styrene/butadiene rubber product |
| DE3839940A1 (en) * | 1988-11-26 | 1990-05-31 | Stockhausen Chem Fab Gmbh | Aqueous polyurethane and polyurethane-urea dispersions, and process for the flocking of elastomeric mouldings using these dispersions |
| DE4037189A1 (en) * | 1990-11-22 | 1992-05-27 | Bayerische Motoren Werke Ag | Polyurethane foam mouldings for painting - produce surfaces free from defects if coated with resin which cures in presence of hoisting and only then given paint coating |
| JPH04272824A (en) * | 1991-02-28 | 1992-09-29 | Kinugawa Rubber Ind Co Ltd | Weatherstrip and its manufacture |
| DE10358932A1 (en) * | 2002-12-17 | 2005-07-28 | Henkel Kgaa | Production of polyurethane prepolymers with isocyanate end groups, useful for the production of one- or two-component adhesive/sealants, comprises mixing an unsymmetrical diisocyanate and a polyol in the presence of a carboxylic acid amide |
| CN111393607A (en) * | 2020-05-07 | 2020-07-10 | 江苏铁锚玻璃股份有限公司 | Formula of thermoplastic polyurethane elastomer rubber sheet and extrusion molding method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1405257A (en) * | 1972-05-10 | 1975-09-10 | Dunlop Ltd | Method of producing multicomponent articles |
| AU464814B2 (en) * | 1973-01-26 | 1975-09-04 | Bridgestone Tire Company Limited | A method for improving the adhering ability of vulcanized rubber surfaces |
| NL7309001A (en) * | 1973-06-28 | 1974-12-31 | ||
| US3991255A (en) * | 1975-01-09 | 1976-11-09 | Uniroyal Inc. | Adhesion of polyurethane to EPDM elastomer |
| NL176679C (en) * | 1975-06-09 | 1985-05-17 | Akzo Nv | PROCESS FOR COATING A PRE-TREATED, VULKANIZED ARTICLE FROM A POLYALOQUE RUBBER WITH A POLYURETHAN. |
-
1979
- 1979-08-14 DE DE2932866A patent/DE2932866C3/en not_active Expired
-
1980
- 1980-07-29 EP EP80104463A patent/EP0025500A1/en not_active Withdrawn
- 1980-08-13 CA CA000358139A patent/CA1143612A/en not_active Expired
- 1980-08-13 JP JP11156380A patent/JPS5634442A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668323A (en) * | 1984-04-17 | 1987-05-26 | Uniroyal Englebert Textilcord S.A. | Method of making flexible, fiber-covered, sheet-like textile article |
| US4596725A (en) * | 1984-05-04 | 1986-06-24 | Henkel Kommanditgesellschaft Auf Aktien | Polyurethane insulating foam |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2932866C3 (en) | 1982-05-19 |
| DE2932866B2 (en) | 1981-08-06 |
| JPS5634442A (en) | 1981-04-06 |
| DE2932866A1 (en) | 1981-02-26 |
| EP0025500A1 (en) | 1981-03-25 |
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