JPS6310645A - Rubber composition - Google Patents

Abstract

PURPOSE:To provide a rubber compsn, which gives a tire tread having excellent grip in high-speed traveling, by blending natural and/or synthetic rubber with an imidazole compd. and/or an imidazoline compd. CONSTITUTION:100pts.wt. rubber (A) composed of natural and/or synthetic rubber (e.g., synthetic polyisoprene rubber) is blended with 0.1-50pts.wt. imidazole compd. (B) of formula I, II or III [where R1, R2, R3, R4 and R5 are each H, a (cyano)alkyl, benzyl, alkyl, sulfonyl, carbonyl, silyl, nitro, halogen, SH or a group of formula IV, V, VI or VII (wherein n and m are each a number of 1-20); and X is halogen] and/or imidazoline compd. of formula VIII.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a comb composition that can be applied to various rubber products such as tires, root protection rubber, and fender materials. The present invention relates to a rubber composition suitable for tread P of a pneumatic tire having grip performance.

(Prior art) Recently, with the improvement in the performance of automobiles, the paving of roads, and the development of expressway networks, 7′? , the demand for pneumatic tires has become stronger, with grip performance being an especially important required characteristic, 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 performance, a styrene-butadiene copolymer rubber with a high styrene content (rubber with a high glass transition temperature) was selected as a tire tread rubber composition, or process oil and cardan black were selected. It was necessary to select a highly filled compounding system and increase the -δ value of the rubber composition.

Furthermore, as a method for improving grip performance deterioration due to temperature rise, Japanese Patent Application Laid-Open No. 187011/1983 describes a method for replacing monomers such as 1,3-butadiene, styrene, or imprene with diethyl phosphate or diphenyl-2-methacryloyl. It is described that a copolymer compound obtained by copolymerizing an acrylate or methacrylate compound containing a diphenyl phosphate group such as diphenyl-2-acryloyloxyethyl phosphate is used.

(Problem to be solved by the invention) However, in order to obtain high grip performance, styrene
If the total styrene content of the butadiene copolymer is increased, the grip performance will certainly increase, but as the temperature of the rubber increases during tire running, the -δ value will decrease, and the grip performance will drop rapidly. There were some problems. On the other hand, although jigrip performance can be improved by high filling of process oil or carden black, there is a limit to how high the filling can be done, and there is a problem in that high filling of these will significantly reduce fracture properties and wear resistance. Japanese Unexamined Patent Publication No. 59-187 to improve the above-mentioned deterioration in grip performance due to temperature rise
The method of No. 011 is not a fool that cannot be applied to natural combs, but has the problem that depending on the manufacturing conditions, the inherent properties of polymers such as styrene-butadiene copolymer combs and derrick diene combs may be impaired. was there.

(Means for Solving the Problems) In order to solve the above problems, the inventors of the present invention have discovered a method of solving the problems as a result of intensive studies, and have already discovered a method for solving the problems described above.
O-163831)'5 is being carried out.

The present invention is also the result of a series of studies, and it has been confirmed that this problem can be solved by blending a specific amount of an imidazole compound and/or an imidazoline compound into the rubber component. That is, 1 the present invention provides 0.1 to 5 parts by weight of an imidazole compound and/or an imidazoline compound to 100 parts by weight of a rubber component consisting of natural comb and/or synthetic rubber.
This is a comb composition characterized by containing 0 parts by weight.

Although the imidazole compounds and imidazolylated compounds 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 25R3 (wherein at least one of R1a R2e R3e R4* R5 is a hydrogen atom, an alkyl group, or a cyanoalkyl group.

benzy, A4t71J group, sulfonyl group, cargenyl group, silyl group, nitro group, halogen atom, mercapto group, -(CN2)n-0-(CH2)mCN, -(
CH2)nOH.

Preferably, X is a halogen atom, and a compound represented by a and m = 1 to 20 f: shown.

Further, the imidazoline compound has the following general formula (wherein R1*
R2@R5* At least one of Rs is a hydrogen atom, an alkyl group, a cyanoalkyl group, a 7L' group, 7
r) Ru group, sulfonyl group, carmenyl group, silyl group, nitro group, halogen atom, mercapto group #-(CH2
), -0-(CH2)0. CN, -(CH2)
nOH.

Compounds represented by are preferred.

In the present invention, as the rubber component, natural rubber or synthetic rubber may be used alone or in combination. Also, as an example of this synthetic rubber, is it synthetic? Lysoglen rubber? Ributadiene rubber' and styrene-butadiene rubber are abundant.

Next, the imidazole compound used in the present invention and/or
-Illustrate examples of imidazoline compounds.

That is, as the imidazole compound of type (1), 2
Methylimidazole (2MZ), 2-undecylimidazole (CIIZ), 2-heptadecyl imidazole (CI7Z), 2-7 enylimidazole (2
pz ), 2-ethyl-4-methylimidazole (2E
4), 2-7enyl-4-methylimidazole (2P
4MZ), 1-benzyl-2-methylimidazole (
IB2■D, 1-cyanoethyl-2-methylimidazo-
N(2MZ-CN), 1-cyanoethyl undecyl imidazole (C112-CN), 1-cyanoethyl-2-phenylimidazole (2PZ-CN), l-
Cyanoethyl-2ethyl-4methylimidazole (2E
4 parts-〇N), 2,4-diamino-6(2'methylimidazolyl(f))ethyl-8-triazine(2MZ-
AZINE), 2,4-diamino-6(τundecylimidazolyl(f))ethyl-8-)riazine(C
IIZ-AZINE), 2,4-diamino-6(2'
Ethyl-4methylimidazolyl-(1'))ethyl-
8-) Riajin (2P4 criminal-AZINE), 1-(P)
luenesulfonyl)imidazo-#(PTZ), 2,4.
5-trif-romoimidazole (TBZ), 4-methylimidazole (4-methyl), N-trimethylcrylimidazole (rough), 2-mercapto-1-methylimidazole (
IM2MrZ), p-(imidazo-, A/-1-yl
) Pheno-# (42P), N-acetylimidazo-# (IAZ), urocanic acid (U-Acid λ imidazole 4,5 sol M 7 @ (ZD-Acid
), 1-(2,4,6-)limethylbenzenesulfoel)imidazole, 2-methyl-5-nitro-1-imidazole ethanol (mm), 2-nitroimidazole, 4-phenylimidazole, l, r- Carbunyldiimidazole, 4,5-diphenylimidazole, 2.2
'-dithiobis(4-dasharbutyl-1-isoglobylimidazole), ethifiv-4-methyl-5-imidazolecarboxylate, histidine, 2-phenyl-4,5-dioxymethylimidazole (2P)tZ
), 2-pheniN-4-methyl-5-oxymethylimidazole (2P4MH2), imidazoleridium deripatip, 4'-(imidazole-i-yt)-azetophenone, 1-methylimidazole, 2-methylimidazole, 4 -methylimidazole, l,1'-thiocarbnyldiimidazole,
1-(2,4,6-)lyisoglopylbenzenesulfonyl)imidazole, 2,4.5-)diphenylimidazole, 1-vinylimidazole, Nω-acetylhistamine, Nα-acetyl-L-histidine monohydrate, L-carnosine, N-)lans-cinnamoylimidazole, 2,4-dimethylimidazole, 1,2-
Dimethylimidazole, 4,5-diphenyA/-2-
Imidazolethiol, 2-ethylimidazole, 2-
Ethyl-4-methylimidazole, N,N'-bis(3
-(4,5-dihydro-IH-imidazole-2-71
)-phenyl] uriazi f lobanaut, 2.2'-
Examples include bis(4,5-dimethylimidazole) and 1-benzylimidazole.

Next, as the imidazole compound of (II) ffl, 1-cyanoethyl-2-methylimidazole-trimelitite (2MZ-CNS), 1-cyanoethyl-2-phenylimidazole-trimelitite (2PZ)
-CNS), 1-cyanoethyl-2/decylimidazole trimellitite (CIIZ-CNS), 1-Schiff/ethyl-2-ethyl-4-methylimidazole trimellitite (2P4MZ-CNS), and the like.

Furthermore, as the imidazole compound of (1) W,
1-Dodecyl-2-methyl-3benzylimidazolium-chloride (SFZ), 1.3dibenzyl-2-
Methylimidazolicum chloride (FFZ).

4-(Hydroxymethyl) imidazole hydrochloride, 4-imidazole acetic acid hydrochloride, 2-methylthio-2-imidazoline hydrochloride, 2-(1-naphthylmethyl-2-imidazoline hydrochloride, tolazoline hydrochloride, propyl- dz-1-(1-phenylethyl/L/
) imidazole-5-carboxylate hydrochloride, etc.

Examples of imidazoline compounds include 2-methylimidazoline (2MZL) and 2-phenylimidazoline (2PZL). Note that these compounds may be used alone or in combination of two or more.

In the present invention, the compounding amount of these compounds is 100% of the rubber component.
The reason why the amount is specified as 0.1 to 50 parts by weight is that if the amount is less than 0.1 part by weight, the desired effect aimed at by the present invention cannot be obtained.

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

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

(Action) The imidazole compound used in the present invention and/or
Or, the imidazoline compound has a rubber molecule and a comb molecule,
It has the effect of increasing the interaction between rubber molecules and filler particles (particularly carton plack particles) and between filler particles, and this allows for large taIIa to be generated even at high temperatures.
Although it has a value of 5, it is possible to obtain a quintuple acid.

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

37.5 parts by weight of Ashi Maoi #15AF Carno Black 65 per 100 parts by weight of styrene-butadiene rubber
1,3-diphenylguanidine, 2-mercaptobenzothiazole together with various imidazole compounds or double parts of 2-7 enylimidazoline (2PZL) to a composition containing 1 part by weight and 3 parts by weight of zinc white. and sulfur were mixed in varying amounts, and each was vulcanized to approximately equal modulus and lath. For each vulcanizate obtained, dynamic strain 1 was measured using a viscoelasticity measurement test manufactured by Rheometrics.
% at 80°C. The results obtained are shown in Table 1 below.

Here, Examples 1 to 27 are (ri-type imidazole compounds,
Examples 28 to 31 show cases of (n)-type imidazole compounds, and Example 32 shows cases of (III) W-type imidazole compounds.

In addition, the case where the imidazole compound or 2-7 enyl imimezoline is not blended is also evaluated in the same way.
It is also shown in the table as Comparative Example 1.

From the results in Table 1, the values of -δ in the high temperature range are found to be larger in all of the Group 5 oxides of the present invention shown in Examples than in the Group 5 oxides of Comparative Example 1. I understand.

Styrene-butadiene rubber 10 with a styrene content of 35%
0 parts by weight of I SAF Cargen Black 80 parts by weight, aroma oil 100 parts by weight, stearin brew 1 part by weight,
Anti-aging agent (IPPD) 1 part by weight, zinc white 3 parts by weight,
0.3 parts by weight of accelerator DPG, 0.7 parts by weight of accelerator DM, and 1.5 parts by weight of sulfur were blended into a P-5 group acid, 2P4MZ, 2PZ-CN, 4
M, 2PH2-CN.

Or U-Aeidt - 5 parts by weight of each of the 5 parts by weight of the comb composition, and 2P4MZ and SFZ t - 3 parts by weight of each of the comb compositions were used to make the tread part - size 2051515-. 13 (for front wheel), 2251
A tire of 515-13 (for rear wheels) was manufactured.

These tires were run as fast as possible on Circula 11, which starts from 4.41 km per lap, and the lap times of the 10th to 20th laps were measured to determine the worst time at that time. In addition, the pest lap times of the 10th to 20th laps of the next tire (Comparative Example 2) produced in the same manner as in the above-mentioned Example without blending the specific imidazole compound or imidazoline compound in the present invention were determined, and this was t-100. The results are shown in Table 2.

The higher the value, the faster the lap time and the better the grip performance at high speeds.

From the results in Table 2, it can be seen that the grip performance of the systems containing the compound of the present invention is greater than that of the systems without the compound.

(Effects of the Invention) As explained above, the comb composition of the present invention can be used in a high temperature range by blending a specific amount of a specific imidazole compound and/or imidazoline compound into the comb component. The δ value increases. Therefore, when such a comb composition is used particularly in tire treads, it has the excellent effect of suppressing the decrease in -δ value that accompanies the rise in tire temperature due to driving, and improving grip performance during high-speed driving. is obtained.

Procedural amendment January 20, 1988 Commissioner of the Patent Office Black 1) Yu Akira 1, Indication of the case Patent Application No. 152613 of 1988 2, Name of the invention Rubber composition 3, Person making the amendment Case and Relationship Patent Applicant Co., Ltd. Brideston 4, Address Address 5, 1-1, Kyobashi-chome, Chuo-ku, Tokyo 104
, subject of amendment or correction Column 6 of “Detailed description of the invention” in the specification
, Contents of amendment (as attached) 1. Details 4, 13th negative line 18th “Meritito (2E4MZ
-CNS), etc. " should be corrected to "Meritecylimidazole (018C11Z) etc.".

2. On page 16, line 2, "Examples 1 to 33. Comparative Example 1" is corrected to "Example 1 to Comparative Example 1."

3, page 16, line 7, corrected to ``r (2PZL) 02 parts by weight and J wor (2PZL) 00.01 7 and phase Mf''.

4. On page 16, line 15, "Examples 1 to 27" is corrected to "Examples 1 to 27A and 34."

5. 17th negative line 7 “Examples 34 to 39. Comparative example 2”
is corrected to "Examples 35 to 40. Comparative Example 2".

6. Table 1 (continued) and its notes on page 19 of the same, and negative table 2 of page 21 of the same are corrected as follows.

Claims (3)

[Claims] (1) Rubber 1 made of natural rubber and/or synthetic rubber
1. A rubber composition comprising 0.1 to 50 parts by weight of an imidazole compound and/or an imidazoline compound per 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, -COOC_nH_2_n
The rubber composition according to claim 1, which is represented by ＿＋＿1 or ▲a numerical formula, a chemical formula, a table, etc.▼, X is a halogen atom, and n and m=1 to 20). (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.