GB2060650A - Bonding Rubber to Metal - Google Patents
Bonding Rubber to Metal Download PDFInfo
- Publication number
- GB2060650A GB2060650A GB8030518A GB8030518A GB2060650A GB 2060650 A GB2060650 A GB 2060650A GB 8030518 A GB8030518 A GB 8030518A GB 8030518 A GB8030518 A GB 8030518A GB 2060650 A GB2060650 A GB 2060650A
- Authority
- GB
- United Kingdom
- Prior art keywords
- nickel
- composition
- abietate
- ferrous metal
- elastomeric
- 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- Withdrawn
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 24
- 229920001971 elastomer Polymers 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 22
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000000806 elastomer Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 13
- 150000002815 nickel Chemical class 0.000 claims description 6
- 239000013536 elastomeric material Substances 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 2
- 239000007767 bonding agent Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 2
- 230000006866 deterioration Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 15
- 229910001369 Brass Inorganic materials 0.000 description 9
- 239000010951 brass Substances 0.000 description 9
- 150000001868 cobalt Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
Classifications
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Ropes Or Cables (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
An elastomer is bonded to a ferrous metal by the inclusion therein of nickel abietate. Subsequent exposure of the elastomer/ferrous metal assembly to vulcanising conditions serves both to vulcanise the elastomer and to bond the two materials together. The resulting bond has been found to be more resistant to deterioration under hot and humid conditions than one achieved by means of other metal salts. A convenient form of nickel abietate is as the salt of nickel and colophony. The invention has application in the production of tyres.
Description
SPECIFICATION
Adhesive Compositions
The present invention relates to a method of bonding an elastomeric composition to ferrous metal, particularly brass-coated wires of the ferrous metal which may be steel.
Various adhesive compositions are known for forming a bond between elastomeric compounds and ferrous metals, and more specifically brasscoated wires of a ferrous metal. The known adhesive compositions usually contain heavy metal salts and more specifically salts where the metal ion is selected from cobalt, manganese, chromium and nickel. Of the heavy metal salts, those at the moment considered by skilled artisans as being the best for the purpose of obtaining sufficiently high adhesion values between elastomeric compounds and brasscoated wires of a ferrous metal are those of cobalt.
Nickel salts are not considered very efficacious for obtaining high adhesion values between elastomeric compounds and brass-coated wires of a ferrous metal.
It is also known that the use of metal salts for bringing about adhesion between elastomeric compounds and brass-coated wires of a ferrous metal gives rise to a bond, the mechanical strength characteristics of which diminish in the course of time, particularly in hot and humid conditions. This phenomenon may create considerable problems when wires of a ferrous metal embedded in an elastomeric compound form structures which are subjected to demanding working conditions, as in the case of tyres for motor vehicles.
With the aim of soiving this problem of bond strength reduction with time, many tests have been carried out using cobalt salts based upon various acids.
Of the many acids tested for the cobalt salts, those of the resin acids, of the naphthenic acids and other complexes have been tried, but the cobalt salts of these acids show a reduction over a period of time in the bond between the elastomeric compounds and brass-coated ferrous wires in the presence of humidity and heat.
The aim of the present invention is to produce a satisfactory bond between an elastomeric composition and a ferrous material and to minimise the reduction with time in the bond strength, even in hot and humid conditions.
According to the present invention a method of bonding an elastomeric composition to a ferrous metal comprises contacting the elastomeric composition with the ferrous metal in the presence of nickel abietate and then subjecting the assembly to conditions such that the elastomeric composition is vulcanised.
In a preferred embodiment of the present invention the ferrous metal is in the form of a wire and the nickel abietate is added to a crude elastomeric compound containing all the additives considered suitable for the particular use to which the item is to be put. A convenient form of nickel abietate is a salt of nickel and colophony, the latter consisting of 98% abietic acid. Nickel abietate has the following formula:
The amount of nickel abietate used in the method of the present invention is preferably between 1% and 10% by weight and more preferably between 3% and 6% by weight, percentages being based upon 100 parts by weight of the elastomer in the elastomeric composition.
The ferrous metal may be brass-coated i.e.
covered by a layer of copper/zinc alloy and when in the form of a wire for example a plurality of brass-coated steel wires, is normally embedded in the crude elastomeric compound containing the nickel abietate. Embedding of the ferrous metal material in the crude elastomeric compound can be performed in any known way. The complete assembly is then subjected to vulcanising conditions during which, apart from cross-linking of the elastomeric material, the adhesion between the said elastomeric compound and the said brass-coated metal material is also obtained.
The invention is illustrated by the following
Example in which all parts are by weight:
Example
In a conventional manner a compound was prepared having the following formulation:
Parts
Natural rubber or polyisoprene 100
Zinc oxide 10
Stearic acid 1
Carbon black 50
Softener 10
Antioxidant 1
Silica 10
Bonding agents=resorcinol 4
and hexamethylene
tetramine
Accelerator 1
Sulphur 3
During preparation of the compound having the above formulation, 4 parts of a nickel/colophony salt was added.
Using the above formulation containing the nickel/colophony salt in the quantity indicated, two specimens were prepared, each consisting of a small cylinder of elastomeric compound, 8 mm in diameter and 12 mm long (covered on the outside by a resistant structure), along the axis of which a brass-coated steel wire was present.
These specimens were then vulcanised.
One of the specimens was then placed in an atmosphere at 1200 in the presence of steam for a period of 8 hours.
The two specimens were then placed in a dynanometer, subjecting the wire to a force acting in the direction of extraction of the wire from the small cylinder of vulcanised elastomeric material.
The results of the experiments were as follows:
1) In the case of the specimen not subjected to the action of steam and heat, the wire was removed at a load of 490 N.
2) In the case of the specimen subjected to the action of steam and heat in the manner described, the wire was removed at a load of 400 N.
In order to demonstrate the advantages arising from the use of a nickel/colophony salt in respect of the bond between elastomeric compounds and brass-coated metal wires, compared with the use of a cobalt/colophony salt, two other specimens were prepared where the compound used for the small cylinder of elastomeric material was the same as the formulation already given, except that instead of the nickel and colophony salt, 4 parts of a cobalt/colophony salt was added. One of these specimens was then placed in an atmosphere at 1200 in the presence of steam for a period of 8 hours. The two specimens were then placed in a dynanometer, subjecting the wire to a force acting in the direction of extraction of the wire from the small cylinder of vulcanised elastomeric material.
The results of the experiments were as follows:
a) In the case of the specimen not subjected to the action of steam and heat, the wire was again removed at a load of 490 N.
b) In the case of the specimen subjected to the action of steam and heat, the wire was removed at load of 350 N.
In fact, as can be seen from the comparison between the mechanical strength data, after the action of the steam at high temperature has taken effect, higher adhesion values are achieved when using a nickel/colophony salt instead of a cobalt/colophony salt.
These results are considered unexpected in that up to now, technicians in the art have considered nickel as a metal ion not possessing in itself a particular aptitude for preserving the mechanical strength values of bonds over a period of time. We have found however that this opinion is contradicted by our experimental results as described above.
Claims (14)
1. A method of bonding an elastomeric composition to a ferrous metal comprises contacting the elastomeric composition with the ferrous metal in the presence of nickel abietate and then subjecting the assembly to conditions such that the elastomeric composition is vulcanised.
2. A method according to claim 1 wherein the nickel abietate is a salt of nickel and colophony.
3. A method according to claim 1 or 2, wherein the nickel abietate is a component of the elastomeric composition.
4. A method according to claim 3, wherein the nickel abietate is present in the composition in an amount between 1% and 10% by weight based upon 100 parts by weight of the elastomer in the composition.
5. A method according to claim 3, wherein the nickel abietate is present in the composition in an amount between 3% and 6% by weight based upon 100 parts by weight of the elastomer in the composition.
6. A method according to any one of the preceding claims, wherein a copper and zinc alloy is applied to the surface of the ferrous metal with which it is intended that the elastomeric material shall come into contact.
7. A method according to any one of the preceding claims, wherein the elastomeric composition has the following formulation:
Parts
Natural rubber or polyisoprene 100
Zinc oxide 10
Stearic acid 1
Carbon black 50
Softener 10
Antioxidant 1
Silica 10
Bonding agents 4
Accelerator 1
Sulphur 3
Nickel/colophony salt 4
8. A method according to claim 1 and substantially as herein described.
9. A method according to claim 1 with reference to the Example.
10. An elastomeric composition bonded to a ferrous metal by the method according to any one of the preceding claims.
11. An assembly comprising a vulcanised elastomeric composition bonded to a ferrous metal wherein nickel abietate is present.
12. An assembly according to claim 11 wherein the nickel abietate is a salt of nickel and colophony.
13. An assembly according to claim 11 or 12 wherein the nickel abietate is a component of the elastomeric composition.
14. An assembly according to claim 13 wherein the nickel abietate is present in the composition in an amount between 1% and 10% by weight based upon 100 parts by weight of the elastomer in the composition.
1 5. An assembly according to claim 13 wherein the nickel abietate is present in the composition in an amount between 3% and 6% by weight based upon 100 parts by weight of the elastomer in the composition.
1 6. An assembly according to any one of claims 11 to 1 5 wherein the ferrous metal is coated with an alloy of cooper and zinc.
1 7. An assembly according to claim 11 with reference to the Example.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT26545/79A IT1125485B (en) | 1979-10-17 | 1979-10-17 | ADHESIVE COMPOSITION BETWEEN ELASTOMERIC MATERIAL AND FERROUS METALS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2060650A true GB2060650A (en) | 1981-05-07 |
Family
ID=11219739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8030518A Withdrawn GB2060650A (en) | 1979-10-17 | 1980-09-22 | Bonding Rubber to Metal |
Country Status (4)
| Country | Link |
|---|---|
| AU (1) | AU6343380A (en) |
| FR (1) | FR2467876A1 (en) |
| GB (1) | GB2060650A (en) |
| IT (1) | IT1125485B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0067488A1 (en) * | 1981-06-16 | 1982-12-22 | Akzo N.V. | A solid rubber adhesion promoter and a method for improving the adhesion of rubber to metal reinforcing elements embedded therein |
| US4435477A (en) | 1983-07-25 | 1984-03-06 | The Firestone Tire & Rubber Company | Rubber compositions and articles thereof having improved metal adhesion and metal adhesion retention |
| US6169137B1 (en) | 1995-01-20 | 2001-01-02 | Compagnie Generale Des Etablissements Michelin & Cie | Tire having a base of precipitated silica with improved rolling resistance |
| US6215079B1 (en) | 1998-12-28 | 2001-04-10 | Hagleitner Betriebshygiene Ges.M.B.H. & Co. Kg | Pressure controlled time switch |
| USD509322S1 (en) | 2004-06-09 | 2005-09-06 | American Safety Razor Company | Razor with protective cap |
| USD527491S1 (en) | 2004-06-09 | 2006-08-29 | American Safety Razor Company | Razor lube bar |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5141915B2 (en) * | 1972-09-08 | 1976-11-12 | ||
| US3905947A (en) * | 1973-10-10 | 1975-09-16 | Ciba Geigy Corp | Organo-nickel salts as adhesion promotors for vulcanizable elastomers to metals |
-
1979
- 1979-10-17 IT IT26545/79A patent/IT1125485B/en active
-
1980
- 1980-09-22 GB GB8030518A patent/GB2060650A/en not_active Withdrawn
- 1980-10-16 AU AU63433/80A patent/AU6343380A/en not_active Abandoned
- 1980-10-16 FR FR8022131A patent/FR2467876A1/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0067488A1 (en) * | 1981-06-16 | 1982-12-22 | Akzo N.V. | A solid rubber adhesion promoter and a method for improving the adhesion of rubber to metal reinforcing elements embedded therein |
| US4435477A (en) | 1983-07-25 | 1984-03-06 | The Firestone Tire & Rubber Company | Rubber compositions and articles thereof having improved metal adhesion and metal adhesion retention |
| US6169137B1 (en) | 1995-01-20 | 2001-01-02 | Compagnie Generale Des Etablissements Michelin & Cie | Tire having a base of precipitated silica with improved rolling resistance |
| US6215079B1 (en) | 1998-12-28 | 2001-04-10 | Hagleitner Betriebshygiene Ges.M.B.H. & Co. Kg | Pressure controlled time switch |
| USD509322S1 (en) | 2004-06-09 | 2005-09-06 | American Safety Razor Company | Razor with protective cap |
| USD527491S1 (en) | 2004-06-09 | 2006-08-29 | American Safety Razor Company | Razor lube bar |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6343380A (en) | 1981-04-30 |
| IT7926545A0 (en) | 1979-10-17 |
| IT1125485B (en) | 1986-05-14 |
| FR2467876A1 (en) | 1981-04-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |