CA1335387C - Vulcanization activator and process for its production - Google Patents
Vulcanization activator and process for its productionInfo
- Publication number
- CA1335387C CA1335387C CA 611974 CA611974A CA1335387C CA 1335387 C CA1335387 C CA 1335387C CA 611974 CA611974 CA 611974 CA 611974 A CA611974 A CA 611974A CA 1335387 C CA1335387 C CA 1335387C
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- carboxylic acid
- component
- acid
- group
- 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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Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A vulcanization activator, based on zinc salts of organic car-boxylic acids, for rubber compounds, which may be vulcanized with sulfur, is disclosed. The vulcanization activator includes homogeneous mixed zinc salts of the following acids:
(a) at least one carboxylic acid of the general formula R-COOH, in which R is an alkyl group having 5 to 17 carbon atoms, a cycloalkyl group having 5 to 17 carbon atoms, or an arylalkyl group having 7 to 17 carbon atoms;
and, (b) an aromatic carboxylic acid, in which the molar ratio of component (a) and component (b) of the homogeneous mixed zinc salt is preferably in the range of 1:19 to 19:1.
A process for the preparation of the vulcanization activator of the invention is also disclosed.
(a) at least one carboxylic acid of the general formula R-COOH, in which R is an alkyl group having 5 to 17 carbon atoms, a cycloalkyl group having 5 to 17 carbon atoms, or an arylalkyl group having 7 to 17 carbon atoms;
and, (b) an aromatic carboxylic acid, in which the molar ratio of component (a) and component (b) of the homogeneous mixed zinc salt is preferably in the range of 1:19 to 19:1.
A process for the preparation of the vulcanization activator of the invention is also disclosed.
Description
1 33~387 The present invention relates to a vulcanization activator and a process for its pl~par~lion. More particularly, the present invention relates to a vu'c. ~ Lion activator based on zinc salts of organic carboxylic acids for a rubber mixture to be vulcanized with sulfur.
It is known from Ullmanns Encyklopadie der technischen Chemie, vol. 9, 1957, p. 387, that the system rubber-sulfur-accelerator zinc oxide can be additionally activated by adding fatty acids, such as stearic acid or zinc salts of fatty acids, such as zinc stearate or zinc laurate. These activators lead to an additional improvement in the mechanical characteris-tics of the vulcanizers and, in part, to a shortening of the vulcanization time.In addition, fatty acids and fatty acid salts lead to an improvement in the processibility and, often, to a delayed start to vl~'c-ni~lion, as well.
It is further known from R.F. Grossman et al Rubber and Plastic News, 1987, how to use zinc salts of an aromatic carboxylic acid, such as, e.g., terephathalic acid. However, due to the high melting point thereof, it is only generally possible to prepare the same by precipitation. Moreover, zinc salts of such aromatic carboxylic acid are often difficult to homogeneously .
disperse in the rubber compound.
It is, Ihere~ore, an object of the present invention to provide an improved vulcanization activator, which can be homogeneously dispersed in rubber and which provides a longer reversion time and a higher elastic modulus during vulc~ni~alion.
It is a further object of the present invention to provide a process for the expeditious preparation of a vulcanization activator which can be easily pelletized.
It has surprisingly been discovered that the foregoing and related objects are accomplished by a vulcanization activator of mixed zinc C salts of a carboxylic acid, or a carboxylic acid mixture, of the general formula R-COOH, in which R stands for an alkyl, cycloalkyl or arylalkyl radical with 5 ~7) to 17 and, prefe rably, 7 to 11 carbon atoms, and further of an aromatic ~ ~ f.
: :~'''""' ,' 1 3353~7 carboxylic acid. The vl ~' ankdlion activator can be prepared as a homo-genous material and can be dispersed in a homogeneous manner in the rubber. Compared with the activators known to the prior art, such as stearic acid, zinc stearate and zinc-2-ethyl capronate, the activator of the present invention gives longer reversion times during vulcanization and supplies vulc-ni~ales with a higher elasticity modulus. In addition, the vu'csnkdles have a reduced compression set, a higher thermal stability, and a beKer dynamic loadability.
The process, according to the invention, involves reacting 1 to 1.5 moles of zinc oxide, zinc hydroxide or zinc carbonate with 2 moles of a carboxylic acid mixture comprising 0.1 to 1.9 mole of carboxylic acid or a carboxylic acid mixture of the aforementioned formula and 0.1 to 1.9 mole of an aromatic carboxylic acid; particular preference being given to benzoic acid or substit~ ~ted benzoic acids, such as, e.g., chlorobenzoic acid or methylbe" ~ c acid. Other suitable aromatic carboxylic acids are of a polycyclic nature, such as, e.g., naphthoic acid and the substitution products thereof, as well as carboxylic acids of heterocyclic aromatics.
Generally, the carboxylic acid mixture is heated to a tempera-ture of 100 to 200OC and is reacted with the zinc compound while mixing under stirring. The volatile reaction products or by-products, such as water and/or carbon dioxide, are thereby removed. Following the cooling of the melt, hard wax-like products are obtained, which can be pelletized or filled from the melt in conventional i"~lc'l~liQns.
The present invention will now be described in greater detail, with reference being made to the following examples, which further include re~rence to the accompanying drawing figure and tables, which illustrate the results of comparison testing procedures.
It should be understood, however, that the accompanying e~d",~'~s and test results are intended as being merely illustrative of the present invention and are not intended as defining the scope thereof.
It is known from Ullmanns Encyklopadie der technischen Chemie, vol. 9, 1957, p. 387, that the system rubber-sulfur-accelerator zinc oxide can be additionally activated by adding fatty acids, such as stearic acid or zinc salts of fatty acids, such as zinc stearate or zinc laurate. These activators lead to an additional improvement in the mechanical characteris-tics of the vulcanizers and, in part, to a shortening of the vulcanization time.In addition, fatty acids and fatty acid salts lead to an improvement in the processibility and, often, to a delayed start to vl~'c-ni~lion, as well.
It is further known from R.F. Grossman et al Rubber and Plastic News, 1987, how to use zinc salts of an aromatic carboxylic acid, such as, e.g., terephathalic acid. However, due to the high melting point thereof, it is only generally possible to prepare the same by precipitation. Moreover, zinc salts of such aromatic carboxylic acid are often difficult to homogeneously .
disperse in the rubber compound.
It is, Ihere~ore, an object of the present invention to provide an improved vulcanization activator, which can be homogeneously dispersed in rubber and which provides a longer reversion time and a higher elastic modulus during vulc~ni~alion.
It is a further object of the present invention to provide a process for the expeditious preparation of a vulcanization activator which can be easily pelletized.
It has surprisingly been discovered that the foregoing and related objects are accomplished by a vulcanization activator of mixed zinc C salts of a carboxylic acid, or a carboxylic acid mixture, of the general formula R-COOH, in which R stands for an alkyl, cycloalkyl or arylalkyl radical with 5 ~7) to 17 and, prefe rably, 7 to 11 carbon atoms, and further of an aromatic ~ ~ f.
: :~'''""' ,' 1 3353~7 carboxylic acid. The vl ~' ankdlion activator can be prepared as a homo-genous material and can be dispersed in a homogeneous manner in the rubber. Compared with the activators known to the prior art, such as stearic acid, zinc stearate and zinc-2-ethyl capronate, the activator of the present invention gives longer reversion times during vulcanization and supplies vulc-ni~ales with a higher elasticity modulus. In addition, the vu'csnkdles have a reduced compression set, a higher thermal stability, and a beKer dynamic loadability.
The process, according to the invention, involves reacting 1 to 1.5 moles of zinc oxide, zinc hydroxide or zinc carbonate with 2 moles of a carboxylic acid mixture comprising 0.1 to 1.9 mole of carboxylic acid or a carboxylic acid mixture of the aforementioned formula and 0.1 to 1.9 mole of an aromatic carboxylic acid; particular preference being given to benzoic acid or substit~ ~ted benzoic acids, such as, e.g., chlorobenzoic acid or methylbe" ~ c acid. Other suitable aromatic carboxylic acids are of a polycyclic nature, such as, e.g., naphthoic acid and the substitution products thereof, as well as carboxylic acids of heterocyclic aromatics.
Generally, the carboxylic acid mixture is heated to a tempera-ture of 100 to 200OC and is reacted with the zinc compound while mixing under stirring. The volatile reaction products or by-products, such as water and/or carbon dioxide, are thereby removed. Following the cooling of the melt, hard wax-like products are obtained, which can be pelletized or filled from the melt in conventional i"~lc'l~liQns.
The present invention will now be described in greater detail, with reference being made to the following examples, which further include re~rence to the accompanying drawing figure and tables, which illustrate the results of comparison testing procedures.
It should be understood, however, that the accompanying e~d",~'~s and test results are intended as being merely illustrative of the present invention and are not intended as defining the scope thereof.
~ ........................................... ..
1 3353~7 Example 1 1.0 mole of zinc oxide was introduced, accompanied by stirring, into a mixture of 1.4 moles of C" to C,O-coconut fatty acid and 0.6 mole of benzoic acid heated to 150 o C. The resulting mixture was then maintained at this temperature until no further water vapor emerged. The clear melt obtained, following cooling, gave a colorless, brittle material with a drop point of 100C.
Example 2 The procedures described in Example 1 were followed except, in this case, use was made of a mixture of 1.4 mole of a C8 to C,O- coconut fatty acid and 0.6 mole of 2-methylbenzoic acid. A colorless material with a drop point of 99 o C was obtained.
Example 3 The procedures described in Examples 1 and 2 were again followed, however, the carboxylic acid mixture was constituted by a mixture of 1.4 mole of a C~ to C~O-coconut fatty acid and 0.6 mole of 2-chlorobenzoic acid. A colorless material with a drop point of 1030C was obtained.
Example 4 A natural rubber compound with the following formulation was prepared:
Constituents Parts by Weight Natural rubber (RSS 1) 100 Carbon black N-330 40 ZnO 5 Antioxidant (TMQ) Acceler~lor Sulfur 2.5 For (a) comparative activator comprised evaluation, the accele-rator consisled of N-morpholinyl benzothiacyl sulfenamide and the accele-rator activator was comprised, on the one hand, by 1 or 3 or 5 parts by ., ~ ., - weight of stearic acid (tests 1 to 3) and, on the other hand, 1 or 3 or 5 parts by weight of the activator prepared according to Example 1 (tests 4 to 6), as well as 5 parts by weight of an activator according to Example 2 (test 7) and 5 parts by weight of an activator according to Example 3 (test 8).
The physical data are given in the following Table 1, namely:
(a) The vu'c-ni~Lion time at 1600C;
(b) The 300% modulus, measured according to DIN 53 504 in MPa;
(c) The tensile strength according to DIN 53504;
(d) The elongation in percent according to DIN 53504;
(e) The vu'cani~lion data determined at 160C with a Monsanto rheometer, namely:
t2 The scorch time in minutes; the time after which the rotor torque had risen by 2 units was measur-ed;
t~o The time after which 90% of the maximum rotor torque was reached;
t~R The time required by the torque acting on the rotor to drop from the vulcanization optimum (100%) to 95% and corresponding to the rever-sion time.
(f) The reversion stability, measured as the quotient of t65R t~o;
(g) The compression set of the vulcanizate, measured in percent according to DIN 53517;
(h) The dynamic loadability of the vulcanizate determined with a cor"pression flexometer (according to Goodrich);
through the temperature rise of the testpiece following a clearly defined number of deformation cycles at the .. . .
-t ~ 1 33~3~7 given frequency and by the permanent set of the test pieces following the measurement.
It is possible, on the basis of the reversion times measured, to draw conclusions regarding the thermal stability because the overvulcaniza-tion, in principle, represents an anaerobic thermal aging.
Table I clearly shows a consider~ble improvement to the reversion times and the conlpression, set as well as deformation residue, as well as a rise in the moduli. FIG. 1 is a graph of the reversion times of the individual tests 1 to 8.
Table ll shows the improvement of the dynamic loadability, apparent from the lower temperature rise of the test pieces or the longer life of the latter. Conventional activators, such as stearic acid, zinc stearate and zinc-2-ethyl capronate were used for comparison purposes.
The reduced permanent set following the test also reveals the improved dynamic loadability of the vu'c ~ni~les.
While only several embodiments of the present invention have been shown and described, it will be obvious to those of ordinary skill in the art that many modifications may be made to the present invention, without departing from the spirit and scope thereof.
(n Q ~ ~ O
01 u~ æ ~
~
Q ~ O, o Q o C~i ~
e~ ~ O, o U-)l t'~ ~ ~ N Ul m co Q ~
U~
Q ~ d o cr)l u~ ~ ~o N ~3 ~n Q N
Nl ~ ~ ~ N ~) Q U~ C~ ~ 00 .C ~~
~ ~ Q
", Q 5 F '' ~
c ~ 8 8 ~ " 8 1i . ~, .~..... ,~
::: ~ :`:`
TABLE I
(continued) Test 1 2 3 _ 5 _ 7 V~ lion data- Monsanto rheometer, 160C
t2 [min] 2.8 2.8 2.5 2.5 2.3 2.6 2.5 2.3 t90 [min] 8.2 9.0 9.6 8.0 8.9 10.2 10.6 10.2 t95R [min] 28 32 35 28 45 75 85 70 t95R:t90 3.4 3.6 3.6 3.5 5.1 7.4 8.0 6.9 Col l lpression set [%]
at 24 h, 70 O C 38 26 at 24 h, 50OC 23 14 TABLE ll Dynamic Loadability, Measured on the Goodrich Flexometer Chambertemperature [~C] 100 Stroke [in cm x 2.4] 0.175 Static load [in kg x 0.45] 30 Frequency [in s~~] 30 Activator Used (per 5 parts) 0~ Stearic Acid Zn-Stearate Zn-2-ethyl capronate Activator in Ex. 1 Testpiece temperature rise [ o C] w after 2000 seconds 21 23 34 22 ~n after 3000 seconds 25 27(testpiece destroyed) 25 after 6000 seconds 39 41(testpiece destroyed) 30 Testpiece permanent set [%]
after 7200 seconds 33 34(testpiece destroyed) 23 . . .
1 3353~7 Example 1 1.0 mole of zinc oxide was introduced, accompanied by stirring, into a mixture of 1.4 moles of C" to C,O-coconut fatty acid and 0.6 mole of benzoic acid heated to 150 o C. The resulting mixture was then maintained at this temperature until no further water vapor emerged. The clear melt obtained, following cooling, gave a colorless, brittle material with a drop point of 100C.
Example 2 The procedures described in Example 1 were followed except, in this case, use was made of a mixture of 1.4 mole of a C8 to C,O- coconut fatty acid and 0.6 mole of 2-methylbenzoic acid. A colorless material with a drop point of 99 o C was obtained.
Example 3 The procedures described in Examples 1 and 2 were again followed, however, the carboxylic acid mixture was constituted by a mixture of 1.4 mole of a C~ to C~O-coconut fatty acid and 0.6 mole of 2-chlorobenzoic acid. A colorless material with a drop point of 1030C was obtained.
Example 4 A natural rubber compound with the following formulation was prepared:
Constituents Parts by Weight Natural rubber (RSS 1) 100 Carbon black N-330 40 ZnO 5 Antioxidant (TMQ) Acceler~lor Sulfur 2.5 For (a) comparative activator comprised evaluation, the accele-rator consisled of N-morpholinyl benzothiacyl sulfenamide and the accele-rator activator was comprised, on the one hand, by 1 or 3 or 5 parts by ., ~ ., - weight of stearic acid (tests 1 to 3) and, on the other hand, 1 or 3 or 5 parts by weight of the activator prepared according to Example 1 (tests 4 to 6), as well as 5 parts by weight of an activator according to Example 2 (test 7) and 5 parts by weight of an activator according to Example 3 (test 8).
The physical data are given in the following Table 1, namely:
(a) The vu'c-ni~Lion time at 1600C;
(b) The 300% modulus, measured according to DIN 53 504 in MPa;
(c) The tensile strength according to DIN 53504;
(d) The elongation in percent according to DIN 53504;
(e) The vu'cani~lion data determined at 160C with a Monsanto rheometer, namely:
t2 The scorch time in minutes; the time after which the rotor torque had risen by 2 units was measur-ed;
t~o The time after which 90% of the maximum rotor torque was reached;
t~R The time required by the torque acting on the rotor to drop from the vulcanization optimum (100%) to 95% and corresponding to the rever-sion time.
(f) The reversion stability, measured as the quotient of t65R t~o;
(g) The compression set of the vulcanizate, measured in percent according to DIN 53517;
(h) The dynamic loadability of the vulcanizate determined with a cor"pression flexometer (according to Goodrich);
through the temperature rise of the testpiece following a clearly defined number of deformation cycles at the .. . .
-t ~ 1 33~3~7 given frequency and by the permanent set of the test pieces following the measurement.
It is possible, on the basis of the reversion times measured, to draw conclusions regarding the thermal stability because the overvulcaniza-tion, in principle, represents an anaerobic thermal aging.
Table I clearly shows a consider~ble improvement to the reversion times and the conlpression, set as well as deformation residue, as well as a rise in the moduli. FIG. 1 is a graph of the reversion times of the individual tests 1 to 8.
Table ll shows the improvement of the dynamic loadability, apparent from the lower temperature rise of the test pieces or the longer life of the latter. Conventional activators, such as stearic acid, zinc stearate and zinc-2-ethyl capronate were used for comparison purposes.
The reduced permanent set following the test also reveals the improved dynamic loadability of the vu'c ~ni~les.
While only several embodiments of the present invention have been shown and described, it will be obvious to those of ordinary skill in the art that many modifications may be made to the present invention, without departing from the spirit and scope thereof.
(n Q ~ ~ O
01 u~ æ ~
~
Q ~ O, o Q o C~i ~
e~ ~ O, o U-)l t'~ ~ ~ N Ul m co Q ~
U~
Q ~ d o cr)l u~ ~ ~o N ~3 ~n Q N
Nl ~ ~ ~ N ~) Q U~ C~ ~ 00 .C ~~
~ ~ Q
", Q 5 F '' ~
c ~ 8 8 ~ " 8 1i . ~, .~..... ,~
::: ~ :`:`
TABLE I
(continued) Test 1 2 3 _ 5 _ 7 V~ lion data- Monsanto rheometer, 160C
t2 [min] 2.8 2.8 2.5 2.5 2.3 2.6 2.5 2.3 t90 [min] 8.2 9.0 9.6 8.0 8.9 10.2 10.6 10.2 t95R [min] 28 32 35 28 45 75 85 70 t95R:t90 3.4 3.6 3.6 3.5 5.1 7.4 8.0 6.9 Col l lpression set [%]
at 24 h, 70 O C 38 26 at 24 h, 50OC 23 14 TABLE ll Dynamic Loadability, Measured on the Goodrich Flexometer Chambertemperature [~C] 100 Stroke [in cm x 2.4] 0.175 Static load [in kg x 0.45] 30 Frequency [in s~~] 30 Activator Used (per 5 parts) 0~ Stearic Acid Zn-Stearate Zn-2-ethyl capronate Activator in Ex. 1 Testpiece temperature rise [ o C] w after 2000 seconds 21 23 34 22 ~n after 3000 seconds 25 27(testpiece destroyed) 25 after 6000 seconds 39 41(testpiece destroyed) 30 Testpiece permanent set [%]
after 7200 seconds 33 34(testpiece destroyed) 23 . . .
Claims (7)
1. A vulcanization activator for a rubber compound which is capable of being vulcanized with sulfur, said vulcanization activator comprising:
homogeneous mixed zinc salts of the following acids:
(a) of at least one carboxylic acid of the formula R-COOH, wherein R is a radical selected from the group consisting of an alkyl group having 5 to 17 carbon atoms, a cycloalkyl group having 5 to 17 carbon atoms and an arylalkyl group having 7 to 17 carbon atoms; and, (b) of an aromatic carboxylic acid, wherein the molar ratio of said component (a) and said component (b) of said homogeneous mixed zinc salt is 1:19 to 19:1.
homogeneous mixed zinc salts of the following acids:
(a) of at least one carboxylic acid of the formula R-COOH, wherein R is a radical selected from the group consisting of an alkyl group having 5 to 17 carbon atoms, a cycloalkyl group having 5 to 17 carbon atoms and an arylalkyl group having 7 to 17 carbon atoms; and, (b) of an aromatic carboxylic acid, wherein the molar ratio of said component (a) and said component (b) of said homogeneous mixed zinc salt is 1:19 to 19:1.
2. The vulcanization activator according to Claim 1, wherein said component (a) includes a carboxylic acid having an alkyl radical with 7 to 11 carbon atoms.
3. The vulcanization activator according to Claim 1, wherein said aromatic carboxylic acid of said component (b) is benzoic acid or a substituted benzoic acid selected from chlorobenzoic acid and methylbenzoic acid.
4. A process for the preparation of a vulcanization activator for a rubber compound which is capable of being vulcanized with sulfur, comprising the steps of:
heating a mixture to 100°C to 200°C, said mixture including:
(a) at least on carboxylic acid of the formula R-COOH, wherein R is a radical selected from the group consisting of an alkyl group having 5 to 17 carbon atoms, an cylcoalkyl group having 5 to 17 carbon atoms and an arylalkyl group having 7 to 17 carbon atoms; and, (b) an aromatic carboxylic acid, wherein the molar ratio of said component (a) and said component (b) of said homogeneous mixed zinc salts is 1:19 to 19:1; and, reacting said mixture, by mixing, with a member selected from the group consisting of zinc oxide, zinc hydroxide, zinc carbonate and a combination thereof, wherein the mole ratio of said mixture to the zinc compound is 2:1.0-1.5;
and removing the volatile by-products to obtain the final product.
heating a mixture to 100°C to 200°C, said mixture including:
(a) at least on carboxylic acid of the formula R-COOH, wherein R is a radical selected from the group consisting of an alkyl group having 5 to 17 carbon atoms, an cylcoalkyl group having 5 to 17 carbon atoms and an arylalkyl group having 7 to 17 carbon atoms; and, (b) an aromatic carboxylic acid, wherein the molar ratio of said component (a) and said component (b) of said homogeneous mixed zinc salts is 1:19 to 19:1; and, reacting said mixture, by mixing, with a member selected from the group consisting of zinc oxide, zinc hydroxide, zinc carbonate and a combination thereof, wherein the mole ratio of said mixture to the zinc compound is 2:1.0-1.5;
and removing the volatile by-products to obtain the final product.
5. The process according to Claim 4, further comprising the step of pelletizing the solidified material.
6. The process according to Claim 4, wherein said component (a) of said mixture includes a carboxylic acid having an alkyl radical with 7 to 11 carbon atoms.
7. The process according to Claim 4, wherein said component (b) of said mixture includes as aromatic carboxylic acid benzoic acid or a substituted benzoic acid selected from chlorobenzoic acid and methylbenzoic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19883831883 DE3831883C1 (en) | 1988-09-20 | 1988-09-20 | |
| DEP3831883.0 | 1988-09-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1335387C true CA1335387C (en) | 1995-04-25 |
Family
ID=6363308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 611974 Expired - Lifetime CA1335387C (en) | 1988-09-20 | 1989-09-19 | Vulcanization activator and process for its production |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0363562B1 (en) |
| JP (1) | JP2657245B2 (en) |
| CA (1) | CA1335387C (en) |
| DE (1) | DE3831883C1 (en) |
| ES (1) | ES2061792T3 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW223650B (en) * | 1993-06-14 | 1994-05-11 | Akzo Nv | Sulfur-vulcanized rubber compositions |
| JP2002371156A (en) * | 2001-04-10 | 2002-12-26 | Yokohama Rubber Co Ltd:The | Rubber composition |
| JP5079261B2 (en) * | 2006-05-31 | 2012-11-21 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire using the same |
| JP5002194B2 (en) * | 2006-05-31 | 2012-08-15 | 住友ゴム工業株式会社 | Rubber composition for tire and tire using the same |
| JP4540691B2 (en) | 2007-06-08 | 2010-09-08 | 住友ゴム工業株式会社 | Rubber composition for tire and tire |
| JP4638950B2 (en) | 2008-09-01 | 2011-02-23 | 住友ゴム工業株式会社 | Rubber composition for studless tire and studless tire |
| JP5132606B2 (en) * | 2009-02-23 | 2013-01-30 | 台茂高分子科學股▲ふん▼有限公司 | Sulfurization aid |
| JP6575464B2 (en) * | 2016-08-29 | 2019-09-18 | 住友ゴム工業株式会社 | Rubber composition |
| JP6933068B2 (en) * | 2016-09-23 | 2021-09-08 | 住友ゴム工業株式会社 | Rubber composition for steel cord coating and tires |
| JP6977259B2 (en) * | 2016-12-21 | 2021-12-08 | 住友ゴム工業株式会社 | Pneumatic tires |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1142195A (en) * | 1965-06-18 | 1969-02-05 | British Petroleum Co | Alkaline lubricating oil |
| GB2105345B (en) * | 1981-08-18 | 1985-04-03 | British Petroleum Co Plc | A curable rubber composition |
| EP0172410A1 (en) * | 1984-08-24 | 1986-02-26 | The Firestone Tire & Rubber Company | Method for increasing the modulus of vulcanizable rubber |
-
1988
- 1988-09-20 DE DE19883831883 patent/DE3831883C1/de not_active Expired
-
1989
- 1989-06-03 ES ES89110074T patent/ES2061792T3/en not_active Expired - Lifetime
- 1989-06-03 EP EP19890110074 patent/EP0363562B1/en not_active Expired - Lifetime
- 1989-09-19 JP JP1240927A patent/JP2657245B2/en not_active Expired - Fee Related
- 1989-09-19 CA CA 611974 patent/CA1335387C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3831883C1 (en) | 1989-09-21 |
| ES2061792T3 (en) | 1994-12-16 |
| EP0363562A1 (en) | 1990-04-18 |
| JPH02169642A (en) | 1990-06-29 |
| EP0363562B1 (en) | 1994-02-09 |
| JP2657245B2 (en) | 1997-09-24 |
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