GB2350616A - Novolak resins used as bonding agents - Google Patents
Novolak resins used as bonding agents Download PDFInfo
- Publication number
- GB2350616A GB2350616A GB9910271A GB9910271A GB2350616A GB 2350616 A GB2350616 A GB 2350616A GB 9910271 A GB9910271 A GB 9910271A GB 9910271 A GB9910271 A GB 9910271A GB 2350616 A GB2350616 A GB 2350616A
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- GB
- United Kingdom
- Prior art keywords
- novolak resin
- preparing
- phenol
- novolak
- resorcinol
- 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.)
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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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/24—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with mixtures of two or more phenols which are not covered by only one of the groups C08G8/10 - C08G8/20
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/14—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with halogenated phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A bonding agent suitable for use in bonding a substrate to a rubber, wherein the bonding agent comprises a novolak resin in admixture with a latex. The novolak resin is derived from formaldehyde, a phenol and resorcinol, wherein at least one of the phenol or resorcinol components is alkoxylated. A method of preparing such a novolak resin involves the reaction of a phenol with formaldehyde in the presence of an alkaline catalyst to form a resole resin, before reacting the resole resin with resorcinol in the presence of an acid catalyst to form the novolak resin.
Description
2350616 -1 IMPROVEMENTS IN OR RELATING TO BONDING AGENTS This invention
relates to novel compositions of matter suitable for use in improving adhesion between a substrate and a rubber and more particularly, but not exclusively, is concerned with compositions for improving the adhesion between polyamide or polyester fibres, for example in the form of fabrics or cords, and rubbers and in particular between polyamide fabric and hydrogenated nitrile rubber (HNBR).
Bonding agents have long been used in the preparation of rubber/fibre composites in the manufacture of belting, matting, tyres, tyre cord, hoses, pipes, tubes, preformed sheets, and the like.
is Such bonding agents are generally based on mixtures of a rubber latex and resorcinol/formaldehyde condensation products. United Kingdom Patent Specifications No.
GB2101618 and No. 1140528 adequately describe the preparation and use of such bonding agents.
one weakness of conventional bonding agents of this type is their inability to give adequate bond strengths between fabric and rubber, particularly HNBR, at elevated temperatures under conditions of use.
Indeed it is well known that, to achieve the desired levels of adhesion, it is necessary to use high amounts of bonding agent (with consequent brittleness and stiffness effects) or to use a primer coat to assist adhesion or to use a combination of both.
It has surprisingly been found that novel bonding agents based on alkoxylated resorcinol or alkoxylated phenols show improved performance compared with traditional products based on resorcinol itself, or merely alkyl substituted resorcinol.
Accordingly, a first aspect of the present invention provides a novolak resin suitable for use in the preparation of a bonding agent for bonding a substrate to rubber, which novolak resin is derived from formaldehyde, a phenol and resorcinol wherein at least one of the phenol or resorcinol is alkoxylated.
In accordance with a second aspect of the present invention, there is provided a method of preparing the novolak resin of the first aspect of the invention which method comprises reacting the phenol with the formaldehyde in the presence of an alkaline catalyst to form a resole resin and reacting the resole resin with the resorcinol in the presence of an acid catalyst to form the novolak resin.
Suitable alkaline catalysts for use in the preparation of the resole resin are ammonia, potassium hydroxide and, preferably, sodium hydroxide. The is formaldehyde is preferably used in the form of formalin (C37% aqueous formaldehyde solution). The resole forming reaction may be carried out at a temperature of from OOC to 1000C and the molar ratio of formalin and phenol may be about 2:1, preferably 1.85:1. The amount of catalyst may be from about 0.01 to 10, preferably from 2.5 to 5.0, equivalents.
The novolak-forming reaction may similarly be effected at from O'C to 1OCC and the acid catalyst is preferably, but not necessarily, sulphuric acid. other suitable acid catalysts are hydrochloric acid, nitric acid, formic acid, oxalic acid, acetic acid, and 1D-toluene sulphonic acid. The molar ratio of the resole and the resorcinol is preferably, but not necessarily, from about 1:1 to 1:2.
Suitable substituted and un-substituted phenols used in the preparation of the resole may have the general formula:
R 2- X c 3 (2,,- k where X can be OH, SH or where Y 0 or S, R' H, CH3. C2H. or C3H7, n 1 to 5, and R2, R3, R", R' and R 6 can independently be H, C, to C,0 alkyl, methoxy, ethoxy, Cl, Br or I.
Preferably, the phenol is 4-chlorophenol.
Examples of suitable alkoxylated resorcinols are:
,7,,7, 90.
where Z can be:
C)_ c)4 - J -n where R' = H, CH3. C2H. or C3H7 r n = 1 to 5, and R7, R8, Rg, and RIO can independently be H or halogen such as Br or Cl, or C, to C, alkyl.
Preferably, the alkoxylated phenol is 1,3(2- hydroxyethoxy) benzene.
The final novolak preparation can be used on its own or in a solution or dispersion in a suitable media.
The solution is preferably, but not necessarily, an aqueous solution prepared by first isolating the novolak from the reaction mix, washing the novolak and then dissolving it in alkaline water. The alkali is preferably, but not necessarily, monoethanolamine.
other suitable alkalis for use in the preparation of the final aqueous solution include ammonia, diethanolamine, triethanolamine, triethylamine, dime thyl aminoethanol, butylamine, propylamine, dibutylamine, and tributylamine. The level of alkali to novolak in solution is preferably, but not necessarily, from about 1.2 to 1.5 equivalents of alkali per equivalent of novolak.
In an alternative method of preparing the desired novolak resin, the novolak resin or the resole resin may be alkoxylated in situ at any suitable stage instead of using alkoxylated phenol or alkoxylated resorcinol. In this case, the phenol used in the preparation of the resole resin may be, for example, 2-(4-chlorophenoxy) ethanol.
The final aqueous novolak solution may be used, with a suitable latex, to produce the desired bonding agent.
Accordingly, a third aspect of the present invention provides a bonding agent suitable for use in bonding a substrate to a rubber which bonding agent comprises the novolak resin of the first aspect of the invention in admixture with a latex.
- Generally, the latex is in the form of a resorc inol / formal in/ latex dip (RFL) which typically may have the following formulation:- Component Weight% Formaldehyde 36% 1.47 Resorcinol 2.16 Sodium Hydroxide 20% 0.25 Water 39.91 HNBR Latex 51.26 Antioxidant 1.05 Carbon Black 3.90 The final aqueous novolak solution may be used as follows:
It is first mixed with an aqueous RFL dip comprising a resorcinol-formaldehyde polymer and a rubber latex (e.g. having the above composition), and the mixture is then applied to the fabric or other substrate by a dipping or spreading process. The dipped substrate is then heat treated under tension at a temperature in the region of from about 100 to 2800C, preferably from about 200-2500C for a period of from about 10 to 150 seconds, preferably from about 60-120 seconds,in an air drying oven. This is then subsequently bonded to the rubber by sandwiching the uncured rubber between two strips of the aforementioned treated substrate. This is then placed in a cavity mould (preheated to 153 + 20C) and cured in a hydraulic press f or a period of 30 t 5 minutes at a pressure of approximately 5 tons per square inch.
It has been found that the bonding agents of the invention can increase the adhesion between fabric and rubber by as much as 50% and in some cases can eliminate the necessity of using a primer.
The bonding agent is suitable for improving the adhesion between various substrates and rubbers. Thus, the substrate can be a metal; a polymer; a woven or non-woven material; a cord; a thread; a synthetic fibre or filament such as rayon, glass, carbon, polyester, polyamide, and aramid; a natural fibre such as cotton; and glass, etc. The rubber can be natural or synthetic, including acrylonitrile/butadiene/ styrene, acrylic rubber, polyether urethane rubber, polyester urethane rubber, butadiene rubber, chloroprene rubber, ethylene propylene diene rubber, f luoro rubber (FKM and FPM), hydrogenated acrylonitrile butadiene (nitrile) rubber, butyl rubber, acrylonitrile butadiene (nitrile) rubber, silicone rubber, styrene butadiene rubber, styrene butadiene styrene copolymer, styrene ethylene butadiene styrene, styrene isoprene styrene, Standard Malaysian rubber, polysulphide rubber, crosslinked acrylonitrile butadiene (nitrile) rubber, and neoprene.
7- The following Examples illustrate the invention Example 1
134g of 4chlorophenol were dissolved in 393g of water with 128g of 32% sodium hydroxide. This solution was heated to SO'C. To this solution were added 159g of 37% aqueous formaldehyde solution. The solution was then heated to 800C and maintained at this temperature for 1 hour. The solution was then cooled to 550C.
250g of 1,3 bis (2-hydroxyethoxy) benzene were added along with 189g water. This solution was acidified to pH 1 with 98% sulphuric acid and heated to 900C and maintained at this temperature for 3% hours during which time an orange precipitate formed. This precipitate was isolated, slurried and washed with cold water to remove any residual salt. The precipitated product was then dissolved in 493g of monoethanolamine and 1027g water at a temperature of 350C.
ExamiDle 2 Example 1 was repeated with the 4-chlorophenol replaced by 4-bromophenol on an equimolar basis.
ExamiDle 3 Example 1 was repeated with 25% of the 4 chlorophenol replaced by a molar equivalent of parachlorometaxylenol. A red fusible product was obtained which was dissolved in 5N aqueous ammonia.
Example 4
Example 1 was repeated with 50% of the 1,3- (2 hydroxyethoxy) benzene replaced by a molar equivalent of resorcinol. The resultant fusible product was dissolved in 5N aqueous ammonia.
Example 5 5
As a comparison, Example 1 was repeated using resorcinol instead of the alkoxy substituted resorcinol.
The novolak solutions obtained in these Examples were each admixed with an RFL dip of the aforementioned composition and used as a bonding agent in the manner previously described to adhere polyamide fabric to HNBR rubber. The adhesion in each case was measured by peeling the formed fabric reinforced rubber strips (dimensions 175mm by 25.4mm by 5mm) in a suitable tensile tester using a ikN load cell at a crosshead speed of 100 mm/min. The peel strength was recorded in N/25.4mm.
The results are shown in the following Table.
Sample Peel strength (N/25.4mm) Without bonding agent 120 Example 1 340
Example 2 250
Example 3 220
Example 4 290
Example 5 225
The Table also shows the result obtained when the RFL dip alone was used (i.e. when no novel novolak was present).
9_
Claims (25)
1. A novolak resin suitable for use in the preparation of a bonding agent for bonding a substrate to rubber, which novolak resin is derived from formaldehyde, a phenol and resorcinol, wherein at least one of the phenol or resorcinol is alkoxylated.
2. A novolak resin according to claim 1, wherein the phenol has the general formula:
R 2 X gh ' Q P1.
where X is OH, SH or R 1 - - Y OH n where Y = 0 or S, 1 R H, CH3. C2H5 or C3H7 n 1 to 5, and 2 3 4 5 6 R ' R ' R, R and R are independently H, C, to C10 alkyl, methoxy, ethoxy, Cl, Br or I.
3. A novolak resin according to claim 2, wherein the phenol is 4chlorophenol.
4. A novolak resin according to claim 1 or 2, wherein the phenol is 1,3-(2-hydroxyethoxy) benzene.
5. A novolak resin according to any of claims 1 to 4, wherein the resorcinol is z k 0)o ec.
where Z is R' -0 OH n where R = H, CH3. C2H. or C3H7.
n = 1 to 5, and 7 8 9 10 R ' R, R, and R are independently H or halogen or Cl to C4 alkyl.
6. A method of preparing a novolak resin comprising reacting a phenol with formaldehyde in the presence of an alkaline catalyst to form a resole resin and reacting the resole resin with resorcinol in the presence of an acid catalyst to form the novolak resin, wherein at least one of the phenol or resorcinol is alkoxylated.
7. A method of preparing a novolak resin according to claim 6, wherein the alkaline catalyst for the preparation of the resole resin is ammonia, potassium hydroxide or sodium hydroxide.
8. A method of preparing a novolak resin according to claim 6 or 7, wherein the formaldehyde is in the form of formalin (@37% aqueous formaldehyde solution) 5
9. A method of preparing a novolak resin according to any of claims 6 to 8, wherein the resoleforming reaction is carried out at a temperature of from OOC to 1000C.
10. A method of preparing a novolak resin according to any of claims 6 to 9, wherein the molar ratio of formalin and phenol is 2:1.
is
11. A method of preparing a novolak resin according to any of claims 6 to 9, wherein the molar ratio of formalin and phenol is 1.85:1.
12. A method of preparing a novolak resin according to any of claims 6 to 11, wherein the amount of catalyst is from 0.01 to 10 equivalents.
13. A method of preparing a novolak resin according to claim 12, wherein the amount of catalyst is from 2.5 to 5.0 equivalents.
14. A method of preparing a novolak resin according to any of claims 6 to 13, wherein the novolak-forming reaction is effected at from OOC to 1000C.
15. A method of preparing a novolak resin according to any of claims 6 to 14, wherein the acid catalyst is sulphuric acid, hydrochloric acid, nitric acid, formic acid, oxalic acid, acetic acid, or ID toluene sulphonic acid.
16. A method of preparing a novolak resin according to any of claims 6 to 15, wherein the molar ratio of the resole and the resorcinol is from 1:1 to 1:2.
17. A method of preparing a novolak resin comprising reacting a phenol with formaldehyde in the presence of an alkaline catalyst to form a resole resin and reacting the resole resin with the resorcinol in the presence of an acid catalyst to form the novolak resin, wherein the novolak resin or the resole resin is alkoxylated in situ.
18. A method of preparing a novolak resin according to claim 17, wherein the phenol is 2-(4 chlorophenoxy) ethanol.
19. A method of preparing a novolak resin substantially as hereinbefore described in any one of Examples 1 to 4.
20. A novolak resin whenever prepared by the method claimed in any one of claims 6 to 19.
21. A novolak resin as claimed in any one of claims 1 to 5 or 20 in the form of an aqueous solution.
22. A novolak resin as claimed in claim 21 wherein the aqueous solution includes, as alkali, monoethanolamine, ammonia, diethanolamine, triethanolamine, triethylamine, dimethylaminoethanol, butylamine, propylamine, dibutylamine or tributylamine.
23. A novolak resin as claimed in claim 22 wherein the level of alkali to novolak in solution is from 1.2 to 1.5 equivalents of alkali per equivalent of novolak.
24. A bonding agent suitable for use in bonding a substrate to a rubber wherein the bonding agent comprises a novolak resin as claimed in any one of claims 21 to 23 in admixture with a latex.
25. A bonding agent as claimed in claim 24 substantially as hereinbefore described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9910271A GB2350616B (en) | 1999-05-04 | 1999-05-04 | Novolak resins used as bonding agents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9910271A GB2350616B (en) | 1999-05-04 | 1999-05-04 | Novolak resins used as bonding agents |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9910271D0 GB9910271D0 (en) | 1999-06-30 |
| GB2350616A true GB2350616A (en) | 2000-12-06 |
| GB2350616B GB2350616B (en) | 2003-07-30 |
Family
ID=10852763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9910271A Expired - Fee Related GB2350616B (en) | 1999-05-04 | 1999-05-04 | Novolak resins used as bonding agents |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2350616B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2384780A (en) * | 2001-12-07 | 2003-08-06 | Thomas Swan & Company Ltd | Primer for bonding fibres to rubbers |
| EP2253649A1 (en) * | 2009-05-21 | 2010-11-24 | Cytec Surface Specialties Germany GmbH & Co. KG | Adhesion-promoting system for rubber goods |
| US10435503B2 (en) | 2017-09-22 | 2019-10-08 | Hexion Inc. | Compositions for polyurethane applications |
| US10604614B2 (en) | 2017-09-22 | 2020-03-31 | Hexion Inc. | Compositions and methods to produce alkoxylated triazine-arylhydroxy-aldehyde condensates |
| US10640475B2 (en) | 2017-09-22 | 2020-05-05 | Hexion Inc. | Compositions and methods to produce alkoxylated triazine-arlhydroxy-aldehyde condensates |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57167312A (en) * | 1981-04-10 | 1982-10-15 | Hodogaya Chem Co Ltd | Production of resorcinol copolymer |
| GB2101618A (en) * | 1981-04-10 | 1983-01-19 | Hodogaya Chemical Co Ltd | Process for preparing resorcinol copolymers |
| GB2192636A (en) * | 1986-07-18 | 1988-01-20 | Tokyo Ohka Kogyo Co Ltd | A positive-working photoresist composition |
| EP0351081A2 (en) * | 1988-06-24 | 1990-01-17 | MITSUI TOATSU CHEMICALS, Inc. | Phenolic resin molding materials |
| EP0384077A2 (en) * | 1989-02-07 | 1990-08-29 | Indspec Chemical Corporation | Process for the preparation of reinforced plastics based on a resorcinol-modified phenolic resin |
| JPH09291249A (en) * | 1996-04-24 | 1997-11-11 | Sakata Corp | Pigment dispersion, photosetting pigment-dispersed resist composition for color filter using the same |
-
1999
- 1999-05-04 GB GB9910271A patent/GB2350616B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57167312A (en) * | 1981-04-10 | 1982-10-15 | Hodogaya Chem Co Ltd | Production of resorcinol copolymer |
| GB2101618A (en) * | 1981-04-10 | 1983-01-19 | Hodogaya Chemical Co Ltd | Process for preparing resorcinol copolymers |
| GB2192636A (en) * | 1986-07-18 | 1988-01-20 | Tokyo Ohka Kogyo Co Ltd | A positive-working photoresist composition |
| EP0351081A2 (en) * | 1988-06-24 | 1990-01-17 | MITSUI TOATSU CHEMICALS, Inc. | Phenolic resin molding materials |
| EP0384077A2 (en) * | 1989-02-07 | 1990-08-29 | Indspec Chemical Corporation | Process for the preparation of reinforced plastics based on a resorcinol-modified phenolic resin |
| JPH09291249A (en) * | 1996-04-24 | 1997-11-11 | Sakata Corp | Pigment dispersion, photosetting pigment-dispersed resist composition for color filter using the same |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2384780A (en) * | 2001-12-07 | 2003-08-06 | Thomas Swan & Company Ltd | Primer for bonding fibres to rubbers |
| GB2384780B (en) * | 2001-12-07 | 2005-12-07 | Thomas Swan & Company Ltd | A method and composition for bonding fibres to rubbers |
| EP2253649A1 (en) * | 2009-05-21 | 2010-11-24 | Cytec Surface Specialties Germany GmbH & Co. KG | Adhesion-promoting system for rubber goods |
| WO2010133622A1 (en) * | 2009-05-21 | 2010-11-25 | Cytec Surface Specialties Germany Gmbh | Adhesion-promoting system for rubber goods |
| CN102459379A (en) * | 2009-05-21 | 2012-05-16 | 氰特表面技术德国有限公司 | Adhesion-promoting system for rubber goods |
| US8759471B2 (en) | 2009-05-21 | 2014-06-24 | Allnex Germany Gmbh | Adhesion-promoting system for rubber goods |
| CN102459379B (en) * | 2009-05-21 | 2014-08-13 | 氰特表面技术德国有限公司 | Adhesion-promoting system for rubber goods |
| EA021682B1 (en) * | 2009-05-21 | 2015-08-31 | Аллнэкс Джермани Гмбх | Adhesion-promoting system for rubber goods |
| US10435503B2 (en) | 2017-09-22 | 2019-10-08 | Hexion Inc. | Compositions for polyurethane applications |
| US10604614B2 (en) | 2017-09-22 | 2020-03-31 | Hexion Inc. | Compositions and methods to produce alkoxylated triazine-arylhydroxy-aldehyde condensates |
| US10640475B2 (en) | 2017-09-22 | 2020-05-05 | Hexion Inc. | Compositions and methods to produce alkoxylated triazine-arlhydroxy-aldehyde condensates |
| US11028219B2 (en) | 2017-09-22 | 2021-06-08 | Hexion Inc. | Compositions for polyurethane applications |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9910271D0 (en) | 1999-06-30 |
| GB2350616B (en) | 2003-07-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20100504 |