JPS63139931A - Rubber composition - Google Patents

Abstract

PURPOSE:To obtain a rubber composition which can give a tire improved in grip during high-speed running, by mixing a rubber component with an imidazole and/or imidazoline compound and a proton acid derivative at a specified weight ratio. CONSTITUTION:100pts.wt. rubber component (A) comprising natural and/or synthetic rubber is mixed with 0.1-50pts.wt. imidazole compound of, e.g., formula I, II or III (wherein R1, R2, R3, R4 and R5 are each H, alkyl, cyanoalkyl, benzyl or the like, and X is a halogen) and/or imidazoline compound (B) of formula IV and 0.1-50pts.wt. proton acid derivative (C) to obtain the purpose rubber composition. Examples of component C include 2,6-di-tert-butyl-p-cresol, acetic acid and benzenesulfonic acid. Since component C is added in this way, scorching which is a defect encountered when component B is added alone can be improved.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a rubber composition that can be applied to various rubber products such as tires, anti-vibration rubber, and fender materials, and particularly relates to a rubber composition that has excellent grip performance. The present invention relates to a rubber composition suitable for a tread of a pneumatic tire.

(Conventional technology) Recently, with the improvement of automobile performance, the paving of roads, and the development of expressway networks, the demand for pneumatic tires with high maneuverability has increased, and grip performance in particular is an essential characteristic. This is typified by acceleration performance and braking performance. Therefore, the higher these characteristics are, the faster, more accurately and safely the vehicle can travel.

Conventionally, in order to obtain high grip properties, a styrene-butadiene copolymer rubber with a high styrene content (rubber with a high glass transition temperature) was selected as the tire's trout rubber composition, or a process oil and carbon black were used with a high content. Select the filled compounding system and check the JAN δ of the rubber composition.
I needed to increase the value.

In addition, as a method for improving grip performance deterioration due to temperature rise, Japanese Patent Application Laid-Open No. 187011/1983 describes a method for improving grip performance due to temperature rise.
It is described that a copolymer rubber obtained by copolymerizing an acrylate or methacrylate compound containing a diphenyl phosphate group such as diphenyl-2-methacryloyloxyethyl phosphate or diphenyl-2-acryloyloxyethyl phosphate is used. There is.

(Problems to be Solved by the Invention) However, when the styrene content of the styrene-butadiene copolymer is increased in order to obtain high grip properties,
Although the grip performance is certainly improved, there is a problem in that the jan δ value decreases as the temperature of the rubber increases due to tire running, and the grip performance rapidly decreases.

On the other hand, although the grip performance can be improved by high filling of process oil or carbon black, there is a limit to how high the filling can be done, and there is a problem in that high filling of these oils causes a significant decrease in fracture properties and wear resistance. In addition, Japanese Patent Application Laid-Open No. 59-18 to improve the grip performance deterioration caused by the temperature rise mentioned above.
The method of No. 7011 not only cannot be applied to natural rubber, but also has the problem that depending on the manufacturing conditions, the original properties of the polymer, such as styrene-butadiene copolymer rubber and polybutadiene rubber, are impaired. From this point of view, the present inventors previously filed Japanese Patent Application No. 16383/1983.
No. 1 and Japanese Patent Application No. 61-39088 proposed that a rubber composition containing an imidazole compound and/or an imidazoline compound could solve the above problems. However, since these imidazole compounds and imidazoline compounds are basic, the rubber composition tends to scorch, resulting in poor workability.

(Means for Solving the Problems) The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems.

In other words, the present invention consists of 0.1 to 50 parts by weight of an imidazole compound and/or imidazosone compound and 0 parts by weight of a proton gradation conductor to 100 parts by weight of rubber made of natural rubber and/or synthetic rubber. .1~50
The present invention relates to a rubber composition characterized in that a ball amount is blended therein.

Although the imidazole compound and imidazoline compound used in the present invention are not limited to those used, the following are particularly preferred.

That is, the imidazole compound has the following general formula:
benzyl group, allyl group, sulfonyl group, carbonyl group,
Silylno^, nitro group, halogen atom, mercapto group,
-(CH2)n-0-(C)12), CN, -(CI
lffi), OH.

-COOCnlltn++ or n and m = 1 to 20) Compounds represented by are preferred.

In addition, the imidazoline compound has the following general formula (wherein R,
, R, , at least one of R, hydrogen atom, alkyl group, cyanoalkyl group, benzyl group, allyl group, sulfonyl group, carbonyl group, silyl group, nitro group, halogen atom, mercapto group, -(C1lz)n-
0-(CHi)-CN, -(C112)nOll.

-COOC, 1I211. , or n and m=1~
20) are preferred.

In the present invention, as the rubber component, natural rubber or synthetic rubber may be used alone or as a blend thereof. Examples of the synthetic rubber include synthetic polyisoprene rubber, polybutadiene rubber, and styrene-butadiene rubber.

Next, the imidazole compound used in the present invention and/or
Alternatively, imidazoline glue is exemplified.

That is, as the imidazole compound of type (I), 2
-Methylimidazole (2MZ), 2-undecylimidazole (CIIZ), 2-heptadecyl imidazole (C17Z), 2-phenylimidazole (2P2)
, 2-ethyl-4-methylimidazole ('2E4M2
), 2-7 x nyl-4-methylimidazole (
2P4MZ), l-benzyl-2-methylimidazo-Jl/(l[12MZ), l-Schiff/ethyl-2-methylimidazole (2MZ-(:N), l-cyanoethyllandecylimidazole (CIIZ-C senior)
, l-cyanoethyl-2-phenylimidazole (2P
Z-[:N), l-cyanoethyl-2ethyl-4methylimidazole (2E4MZ-CN), 2,4-diamino-6-(2'methylimidazolyl(1'))ethyl-s
-Triazine (2) 4Z-AZINE), 2.4-Shifumi) 6- (2”7:/Decylimidazolyl (
1' )) Ethyl-8-triazi:/ (CIIZ-A
zlNE), 2,4-diamino-6-(2'ethyl-4
-Methylimidazolyl(1')ethyl-5-1-! J
7 AZINE (2E4) 12-AZINE), 1-(p)luenesulfonyl)imidazole (PTZ), 2,4.
S-to'J bromoimidazole (TBZ), 4-methyl imiguzole (IIMZ), N-trimethylsilylimidazole (TSZ), 2-mercapto-1
-Methylimidazole IV le (1M2MrZ), p-(imidazole-1-+4)
Fer/-ol (4ZP), N-acetylimidaso Jtz (IAZ), urocanic acid (U-Acid), imidazole 4.5 dicarboxylic acid (ZD-Acid),
1-<2.4.6-trimethylbenzenesulfonyl)imidazole, 2-methyl-5-nitro-1-imidazole ethanol (2MSNIEZ), 2-nitroimidazole, 4-phenylimidazole, 1.1
'-carbonyldiimidazole, 4,5-diphenylimidazole, 2.2'-dithiobis(4-darcialbutyl-1-impropyreimidazole), ethyl-4-methyl-5-imidazole, carboxylate, histidine, 2-phenyl-4,5-dioxymethylimidazole (2PIIZ), 2-phenyl-4-methyl-5-oxydimethylimidazole (2P4 group 117
).

Tylimidazole, 2-methylimidazole, 4-methylimidazole, 1,1'-thiocarbonyldiimidazole, l-(2,4,6-triisopropylbenzenesulfonyl)imidazole, 2,4.5-triphenylimidazole, l -vinylimidazole, N-ω-
Acetylhistamine, N-a-acetyl-histidine monohydrate, L-carnosine, N-)-lance-
Cinnamoylimidazole, 2.4-dimethylimidazole, 1.2-dimethylimidazole, 4.5-diphenyl-2-imitazolethiol, 2-ethylimidazole, 2-ethyl-4-methylimidazole, N, N
'-Bis['3-(4,5-dihydro-IH-imidazole+j/2-μ)-phenyl]uriadipropanate, 2.2'
-bis(4,5-dimethylimidazole), l-pendylimidazole, and the like.

Next, as the imidazole compound of type (II), l
-cyanoethyl-2-methylimidazole-trimelitite (2MZ-CNS), 1-cyanoethyl-2
-phenylimidazole-trinolitite (zPZ-C
NS), l-Schiff/EthiJlz-2'/endecylimidazole trimellitate (CIIZ-CNS)
), 1-cyanoethyl-2ethyl-4-methylimidazo-root')me')tito (2E411Z-CNS),
1.2-diundecylimidazole (2C11Z),
l-stearyl-2-undecylimidazole (C
I8C12Z), etc.

Furthermore, as the imidazole compound of type (m), 1
-Dodecyl-2-methyl-3benzylimidazolium-
Chloride (SFX), 1.3 dibenzyl-2-methylimidazolium-chloride (FFZ), 4-(hydroxymethyl)imidazole hydrochloride, 4
-Imidazole acetic acid hydrochlorite, 2-methylthio-2-imidazoline hydrochloride, 2-(l-naphthylmethyl-2-imidazoline hydrochloride, tolazoline hydrochlorite, propyl-dll-1-(1-phenylethyl ) imidazole-5-carboxylate bitrofluorite, etc.

Examples of imidazoline compounds include 2-methylimidazoline (2MZL) and 2-phenylimidazoline (2MZL).
2P2L)'? I can give it to you. In addition, these compounds are
It may be used alone or in combination of two or more types.

In the present invention, the compounding amount of these compounds is 100% of the rubber component.
The reason why the amount is defined as 0.1 to 50 parts by weight with respect to the amount of water is that if the amount is less than 0.1 fl (1 part), the desired effect of the present invention cannot be obtained.

On the other hand, if it exceeds 50 weight ψ parts, not only will no effect commensurate with the increased weight be obtained, but it will also have an adverse effect on the properties of the product after vulcanization, resulting in unfavorable results.

Further, the protonic acid derivatives used in the present invention include phenol derivatives, carboxylic acid derivatives, sulfonic acid derivatives, sulfuric acid derivatives, phosphorus conductors, cyanuric acid derivatives,
These are sulfinic acid derivatives, nitric acid derivatives, phosphorous m derivatives, dithiophosphoric acid derivatives, and carbonic acid derivatives, specifically 2,
6-tert-butyl-p-cresol, 2.2'
-methylene di-4-methyl-6-tert-butylphenol, 2.5-di-tert-butylhydroquinone, 4.4'-thiobis-3-methyl-6-ter
t-butylphenol, styrenated p-cresol,
4.・1'-Butylidenebis-3-methyl-6-Ler
t-Butylphenol, acetic acid, succinic acid, stearic acid, oleic acid, rosin acid, maleic acid, benzoic acid, p-
Methoxybenzoic acid, p-chlorobenzoic acid, p-nitrobenzoic acid, cinnamic acid, α-naphthylcarboxylic acid, phthalic acid,
Trimellitic acid, pyromellitic acid, phthalic anhydride, benzenesulfonic acid, carbonic acid to 12 alkyl groups, 21
1, benzenesulfonic acid, α-naphthalenesulfonic acid, sulfuric acid, sulfuric acid monomethyl ester, phosphoric acid, phosphoric acid mono(2-ethylhexyl) ester, di(2-ethylhexyl) phosphate, cyanuric acid, cyanuric acid diamide, benzenesulfine acid, p-toluenesulfinic acid, phosphorous acid, summer phosphoric acid dimethyl ester, phosphite diphenyl ester, o,o'-dimethyldithiophosphoric acid, 0
．． Examples include 0'-bis(2-ethylhexyl)dithiophosphoric acid, carbonic acid, and ammonium hydrogencarbonate.

These protonic acid derivatives may be used alone or in combination of two or more, and may be mixed in advance with imidazole or imidazoline compounds when blended into rubber, or may be blended individually or separately. I don't mind.

In addition, in the present invention, in addition to the above-mentioned imidazole compound and/or imidazoline compound and protonic acid derivative, compounding agents commonly used in the rubber industry, such as fillers, softeners, anti-aging agents, and vulcanization accelerators, are used. , a vulcanization accelerator, a vulcanizing agent, etc. can be blended as necessary within the range of usual blending amounts.

(Function) The imidazole compound used in the present invention and/or
Alternatively, when a protonic acid derivative is used in combination with an imidazoline compound, it is possible to improve the scorch property, which was a drawback when an imidazole compound or an imidazoline compound is blended, and to obtain a rubber composition in which the jan δ value at high temperatures is synergistically improved. can.

(Example) Next, the present invention will be explained with reference to Examples and Comparative Examples.

-1 to 22. Examples 1-2 For styrene-butadiene rubber too'@i part.

37.5 parts by weight of aroma oil, 65 parts by weight of 15AF carbon black, 3 parts by weight of zinc white, 1.3 parts by weight of 1,3-diphenylguanidine o, sii, 1.5 parts by weight of dibenzothiazyl disulfide, and 1.5 parts by weight of dibenzothiazyl disulfide. 1-stearyl-2-undecylimidazole (C+aCttZ) or 1-benzyl-2-methylimidazole (IR2
MZ) and various protonic acid derivatives shown in Table 1 at 0. An acid equivalent to the old cell was mixed and kneaded to obtain an unvulcanized rubber composition. For these rubber compositions, the Mooney scorch time at 130°C is 1.1 according to JISK 6300.
was measured. The results are shown in Table 1.

In addition, measurements were also conducted in the case where imidazole and the protonic acid derivative were mixed in advance, and in the case where the protonic acid derivative was not blended as Comparative Examples 1 and 2, and the results are also shown in Table 1.

As is clear from Table 1, when protonic acids are used,
It is clear that the scorch time, which is a drawback when imidazole is added, is improved.

Next, Example 1.3.5.7.9.111.13.14
The unvulcanized rubber composition was vulcanized. For each of the obtained vulcanizates, the Lan δ at 80°C was measured using a viscoelasticity measuring tester manufactured by Rheometrics under the condition of 1% dynamic strain, and the unvulcanized rubber composition of Comparative Example 1 was Similarly, an increase in the jan δ value compared to that measured after vulcanization was determined. The results are shown in Table 2. For comparison, a case in which neither imidazole nor protonic acid derivative was blended was similarly evaluated and shown in Table 2.

As is clear from Table 2, by using imidazole and proton-ugly derivatives together, the janδ
You can see whether the value increases synergistically.

<Effects of the Invention> As explained above, the rubber composition of the present invention is produced by blending a specific amount of a specific imidazole compound and/or imidazoline compound and a specific proton gradation conductor into the rubber component. The scorch property, which was a drawback when compounding the compound, is improved, and the t and an δ values in the high temperature range are synergistically increased. Therefore, when such a rubber composition is used particularly for tire treads, it has the excellent effect of suppressing the decrease in the JAN δ value that accompanies the rise in tire temperature due to driving, and improving the grip property 7 during high-speed driving. or can be obtained.

Procedural amendment July 29, 1988 Mr. Akio Kuroda, Commissioner of the Special Accounts Agency 1. Indication of the case 1986 Patent Application No. 286771 2. The title of the invention is Mu composition 3. Person making the amendment Relationship with the case fF License applicant: Brideston 4, Agent address: 1-1 Kyobashi-chome, Chuo-ku, Tokyo 104 Brideston Patent Department, Osaka Pill Co., Ltd. 6: Number of inventions to be increased due to amendment: None 7: Subject of amendment ( 1) Grasping the “Claims” of the specification (2) Column 8 of “Detailed Description of the Invention” of the specification, contents of amendment; (2,・,,′,,i 1) (1) Specification Page 12, line 7 “X is a halodan atom.”
Delete.

(2) Same page 14, lines 11-14 “2,2'-dithiobis(4-dasharbutyl-1-iso!ropylimidasole), ethyl-4-methy-5-4midazole, cal -xylate" is corrected to "r2,2'-dithiobis(4-tert-butyl-1-ingrobylimidazole), ethyl-4-methyl-5-imidazole xylate."

(3) Same page 15 Correct.

(4) In the same lines 1 and 2, r4'-(imidazol-1-yl)-azetov, non' is replaced with r4'-(imidazol-1-yl)
Corrected to "Acetophenone".

(5) Page 16, lines 4-6 “N, N'-bis[3-(
4,5-nohydroIH-imidazol-2-yl)-
1''N,N'-bis[: 3-(4,5-dihydro-1)I-imidazol-2-yl)-f,nil]urianoglonodanoate ”K corrects.

(6) Direction 111g line “Cl8C12Z J '&
r Corrected to Cl8C11ZJ.

(7) ``4-imidazole acety, quasi, dohydrochloride ~ 2-7. Nylimidazoline (2PZL) e is opened.'' on page 17, lines 5 to 15 of the same page is changed to ``4.
-Imidazole acetic acid, dohyde tetrachloride,! Examples include robi-at-1-(l-), nylether)imidazole-5-force A/&xylate hydrochloride, and the like.

Examples of imidazoline compounds include 2-methylimidazoline (2MZL), 2-7. Nilurochloride, tolazoline hydrochloride, etc. are available. ” is corrected.

(8) "Di(2-ethylhexyl) phosphate" in lines 7-8 of page 19 is corrected to "di(2-ethylhexyl) phosphate".

(9) Item 3 of the claims, "iB line 1'-,

Special IFF Scope (1) Rubber made of natural rubber and/or synthetic rubber 1
01101k>, imidazole compound and/or
Alternatively, a rubber composition characterized in that 0.1 to 50 parts of an imidazoline compound and 0.1 to 50 parts of a proton-stimulating conductor are blended.

(2) The imidazole compound has the following general formula (wherein R1,
At least one of R2, R, In, and R5 is a hydrogen atom, an alkyl group, a cyanoalkyl group, a benzyl group,
Allyl group, sulfonyl group, force/I/f nyl group, silyl group, nitro group, halogen atom, mercapto group, -(C12
), -0-(CH2)rnCN, -(CH2)nO
H.

-〇〇〇〇nH2n+, or m = 1 to 20) %FI: The gum composition according to claim 1.

(3) The imidazoline compound has the following general formula (wherein R
,, R2, R, e R, at least one of which is a water (OH2), -0
-(C12)mCN, -(CH2)nOH.

-COOCnH2,, -Matakes) The rubber composition described in Item 1 of Patent h'#Requested Category 1jJ3.

(4) The gauze assembly according to claim 1, wherein the protonic acid derivative is a phenol-conductor.

(5) The rubber composition according to claim 1, wherein the protonic acid derivative is a calgenic acid conductor.

(6) The rubber composition according to claim 1, in which the protonic acid derivative is a sulfonic acid derivative. (7) The rubber composition according to claim 1, in which the protonic acid hh conductor is a sulfur gradation conductor. thing.

(8) Special feature where the grotonic acid conductor is a phosphoric acid conductor
The rubber composition according to item 1 of Ff requirement category I2111.

(9) The rubber composition according to claim 1, wherein the protonic acid derivative is a cyanuric acid age conductor.

The rubber composition according to claim 1, wherein the atb protonic acid derivative is a sulfine gradation conductor.

Prefecture Protonic acid derivative is special! ff-The rubber composition according to item 1.

α protonic acid derivatives are subdued! ! Il! The one described in item 1 of the 0 range of %FF story, which is a ribbed body, is a 5m bottom one.

斡 The rubber composition according to claim 1, wherein the protonic acid derivative is a dithiophosphoric acid spinner.

The rubber composition according to claim 1, wherein the a→ protonic acid derivative is a carbonic acid vj conductor.

(g) The phenol visiting conductor is 2,6-not-tart-butyl-p-cresol, 2,2'-methylenebis-4'
-Methyl-6-t@rt-butylphenol, 2.5-
Di-ort-butylhydroquinone, 4,4'-thiobis-3-methyl-6-t@rt-butylphenol,
The rubber composition according to item 4 of the specific iFF requirements, which is styrenated-p-cresol, 4,4'-butyrinpi-3-methyl-6-t@rt-butylphenol.

αQ Carboxylic acid sieve conductor is acetic acid, succinic acid, stearic acid, oleic acid, Lono 71S! , maleic acid, benzoic acid, p-methoxybenzoic acid, p-chlorobenzoic acid, p-nitrobenzoic acid, cinnamic acid, α-naphthyl carnoic acid, phthalic acid, trimellitic powder, bilomeri, toric acid, phthalic anhydride The comb composition according to item 5, having a range of 41%.

(122 sulfone IRv!) The rubber composition according to claim 6, wherein the compound is benzenesulfonic acid, benzenesulfonic acid substituted with an alkyl group having 1 to 12 carbon atoms, or α-naphthalenesulfonic acid.

a4 Rubber composition of Mr. FffI #7 J-Muki, in which the sulfuric acid derivative is similar to sulfuric acid monomethyl ester.

(6) Co0 according to item 8 of the scope of the fP phantom search, wherein the phosphoric acid derivative is phosphoric acid, phosphoric acid heptano(2-ethylhexyl) ester, phosphorus fi/(2-ethylhexyl) ester
composition.

10. The plum composition according to item 9, wherein the cyanuric acid I is exclusively cyanuric acid/acid or cyanuric acid diamide.

6! The rubber m-shaped material according to claim 10, wherein the casulfin compound is benzenesulfinic acid or p-toluenesulfinic acid (a) The phosphorous acid derivative is phosphorous acid, phosphorous acid dimethyl ester, phosphorous acid dimethyl ester, or The special feature is phosphorus L-zophenyl ester! eF
The gum composition according to item 12, wherein g# is the desired range.

14. The poum composition according to claim 13, wherein the ditheorin gradation conductor is 0,0'-nomethylzothioline g,o,o'-bis(2-ethylhexyl) ditheorinic acid.

Claims (24)

[Claims] (1) Rubber 1 made of natural rubber and/or synthetic rubber
1. A rubber composition characterized in that 0.1 to 50 parts by weight of an imidazole compound and/or imidazoline compound and 0.1 to 50 parts by weight of a protonic acid derivative are blended with respect to 0.00 parts by weight. (2) The imidazole compound has the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ( In the formula, at least one of R_1, R_2, R_3, R_4, and R_5 is a hydrogen atom, an alkyl group, a cyanoalkyl group, a benzyl group, an allyl group, a sulfonyl group, a carbonyl group, a silyl group, a nitro group, a halogen atom, or a mercapto group. , -(CH_2)_n-O-(CH_2)_mCN
, -(CH_2)_nOH, -COO_nH_2_n_
The rubber composition according to claim 1, which is represented by: (3) The imidazoline compound has the following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, at least one of R_1, R_2, R_3, R_5 is a hydrogen atom, an alkyl group, a cyanoalkyl group,
benzyl group, allyl group, sulfonyl group, carbonyl group,
Silyl group, nitro group, halogen atom, mercapto group, -
(CH_2)_n-O-(CH_2)_mCN, -(C
H_2)_nOH, -COOC_nH_2_n_+_1
or ▲ Numerical formula, chemical formula, table, etc. ▼, X represents a halogen atom, n and m = 1 to 20) The rubber composition according to claim 1. (4) The rubber composition according to claim 1, wherein the protonic acid derivative is a phenol derivative. (5) The rubber composition according to claim 1, wherein the protonic acid derivative is a carboxylic acid derivative. (6) The rubber composition according to claim 1, wherein the protonic acid derivative is a sulfonic acid derivative. (7) The rubber composition according to claim 1, wherein the protonic acid derivative is a sulfuric acid derivative. (8) The rubber composition according to claim 1, wherein the protonic acid derivative is a phosphoric acid derivative. (9) The rubber composition according to claim 1, wherein the protonic acid derivative is a cyanuric acid derivative. (10) The rubber composition according to claim 1, wherein the protonic acid derivative is a sulfinic acid derivative. (11) The rubber composition according to claim 1, wherein the protonic acid derivative is nitric acid. (12) The rubber composition according to claim 1, wherein the protonic acid derivative is a phosphorous acid derivative. (13) The rubber composition according to claim 1, wherein the protonic acid derivative is a dithiophosphoric acid derivative. (14) The rubber composition according to claim 1, wherein the protonic acid derivative is a carbonic acid derivative. (15) The phenol derivative is 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis-4'
-Methyl-6-tert-butylphenol, 2,5-
di-tert-butylhydroquinone, 4,4'-thiobis-3-methyl-6-tert-butylphenol,
The rubber composition according to claim 4, which is styrenated p-cresol and 4,4'-butylidenebis-3-methyl-6-tert-butylphenol. (16) Carboxylic acid derivatives include acetic acid, succinic acid, stearic acid, oleic acid, rosin acid, maleic acid, benzoic acid,
Claim 5 which is p-methoxybenzoic acid, p-chlorobenzoic acid, p-nitrobenzoic acid, cinnamic acid, α-naphthylcarboxylic acid, phthalic acid, trimellitic acid, pyromellitic acid, and phthalic anhydride. The rubber composition described. (17) The rubber composition according to claim 6, wherein the sulfonic acid derivative is benzenesulfonic acid, benzenesulfonic acid substituted with an alkyl group having 1 to 12 carbon atoms, or α-naphthalenesulfonic acid. (18) The rubber composition according to claim 7, wherein the sulfuric acid derivative is sulfuric acid or sulfuric acid monomethyl ester. (19) The rubber composition according to claim 8, wherein the phosphoric acid derivative is phosphoric acid, phosphoric acid mono(2-ethylhexyl) ester, or phosphoric acid di(2-ethylhexyl) ester. (20) The rubber composition according to claim 9, wherein the cyanuric acid derivative is cyanuric acid or cyanuric acid diamide. (21) The sulfinic acid derivative is benzenesulfinic acid,
Claim 10 which is p-toluenesulfinic acid
The rubber composition described in . (22) The rubber composition according to claim 12, wherein the phosphorous acid derivative is phosphorous acid, phosphorous acid dimethyl ester, or phosphorous acid diphenyl ester. (23) The rubber composition according to claim 13, wherein the dithiophosphoric acid derivative is 0,0'-dimethyldithiophosphoric acid or 0,0'-bis(2-ethylhexyl)dithiophosphoric acid. (24) The rubber composition according to claim 14, wherein the carbonic acid derivative is carbonic acid or ammonium bicarbonate.