JPS60262840A - Rubber composition - Google Patents

Abstract

PURPOSE:To provide a rubber compsn. having a higher crosslinking rate and a higher hardness, by incorporating a plurality of particular components in a specific proportion and curing with heating in crosslinking a diene rubber with an org. peroxide. CONSTITUTION:Diene rubber (A), 10-60pts.wt. (meth)acrylic acid metal salt (B) based on 100pts.wt. component A, 0.3-3pts.wt. org. peroxide (C) based on 100pts. wt. total amts. of components A and B, 0.5-10pts.wt. carboxylic acid (metal salt) (D) with does not polymerize by component C based on 100pts.wt. component A, 0-50pts.wt. metal (hydro)oxide (E) based on 100pts.wt. component A, and phenylenebismaleimide (F) are mixed in the wt. ratio of E/F of 10/90-90/10 and cured with heating to give a rubber compsn. A rubber compsn. with a higher crosslinking rate and a higher hardness is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a rubber composition with improved crosslinking speed and hardness.

[Prior Art] A rubber composition obtained by heating and curing a mixture of polybutadiene rubber, α, β-ethylenically unsaturated carboxylic acid, a divalent metal compound, and an organic peroxide exhibits wear resistance. It is known that it is excellent (Japanese Patent Application Laid-Open No. 1211-1989)
1i53, etc.). It is also known that a composition with excellent fracture properties can be obtained by adding a non-polymerizable carboxylic acid or a metal salt of the carboxylic acid to this composition. (See Japanese Patent Publication No. 54-13475, etc.).

[Problems to be Solved by the Invention] However, these compositions are still unsatisfactory in terms of crosslinking speed.

(Means for Solving the Problems) The name of the present invention is based on the results of various investigations to solve the above-mentioned problems. By combining two components of a metal salt of a polymerizable carboxylic acid, a specific non-polymerizable carboxylic acid such as zinc stearate or a specific metal salt thereof, and a specific phenylene hismaleimide in a specific ratio and heat-curing these three components. The present inventors have discovered that the crosslinking rate is improved and the hardness of the resulting product is also improved compared to a rubber composition lacking any one of the following, and has thus completed the present invention.

That is, the present invention has been made to solve the above problems, and includes the following: +C) Organic peroxide (O is 0.3 to 3 parts by weight per 100 parts by weight of the total amount.) td) jc) Carboxylic acid that does not polymerize depending on the component. and/or 1 of the metal salt of this carboxylic acid (Q is +lj)
The amount is 0.5 to 10 parts by weight per 00 parts by weight. ) fil metal oxide and/or metal hydroxide (1@)
The difference between the 100 ゑ parts and the θ~50 hair parts. ) , (+phenylene hismaleimide (+(: / If・
The weight ratio is 10/90 to 90/10. ) Such a mixture is heated and cured to provide a new rubber composition.

The diene rubber that is component (a) of the present invention includes butadiene rubber, styrene-butadiene rubber, etc., and the content of cis-1,4 bond in these rubbers is preferably 30% or more. (1.Metal salt of acrylic acid and/
Or metals for methacrylic acid include zinc,
magnesium.

Examples include aluminum and calcium. Among these, zinc acrylate or zinc methacrylate is preferably used. The amount of ■ added is 10 to 100 double star parts of memory.
It is selected from 60 parts by weight, and if it is less than 10 parts by weight, the crosslinking will be insufficient, and if it is more than 60 parts by weight, it will be too hard and brittle.

Examples of +c organic peroxides include cycumyl peroxide (hereinafter abbreviated as t-DCP), n-butyl-4,4-his-(t-butylperoxy)-herylate, lauroyl peroxide, and benzoyl. peroxide, sheet
-butyl peroxide, 2,5-dimethyl-2,5-
Dialkyl peroxides such as di-t-butylperoxyhexane, α,α'-bis-, t-butylperoxy-p-diisopropylbenzene are used, especially DC
P is commonly used. (The amount of a to be added is selected from 0.3 to 3.0 parts by weight based on the total i of 100 parts by weight. If it is less than 0.03 parts by weight, the elasticity of the rubber composition is too low, If the elastic modulus exceeds 100 m, the elastic modulus is too high and the performance is not good.

Yuno (as a carbonic acid that does not polymerize due to component 0,
Examples include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, and stearic acid, unsaturated fatty acids such as olefinic acid, and aromatic carboxylic acids such as ammonium, θ, and aromatic acid, and metal salts of these carboxylic acids are preferred. used for. In addition,(
+)'+ Acid component During the production of polymerizable carboxylic acid metal salts, these monopolymerizable carboxylic acids are simultaneously charged and reacted with fermented zinc to obtain a mixture of metal salts, which is (-
Preferred types of metal salts that may be used as components b) and (2) include zinc, calcium, magnesium, aluminum, and sodium. The amount of component (i) to be added is selected from 0.5 to 10 parts by weight per 100 parts by weight of component (i).

As the metal in the metal oxide and/or metal hydroxide of re), zinc, magnesium, etc. are used.

The amount of the component added is 0 to 5 per 100 parts by weight of
Selected from 0 parts by weight. That is, in the rubber composition of the present invention, component (e) is not necessarily included, but
Improvements in crosslinking speed and hardness are achievable, but usually ■
100 weights! It is desirable to mix 5 to 30 parts of component (2) to 11 parts.

Examples of the phenylene hismaleimide of f jl include wet-phenylene bismaleimide, P-2 phenylene hismaleimide, N,N'-sithiobisphenylenemaleimide l"'Y
can be mentioned. The amount added is +j)/tJ in weight ratio with ■.
) is 10/90 to 90/10, preferably 50
It is 150-30/70. Also, ■、■ total 9100
ff! It is preferable to add 1 to 5 parts by weight per 1 part of ff, and it is also possible to add carbon black, silica, inorganic fillers, anti-aging agents, etc. that are used in ordinary rubber compounding.

The rubber composition of the present invention can be mixed and cured by a conventional method, and the curing temperature is preferably 110 to 180°C, and the hardness is preferably in the range of JIS 70 to 95 degrees.

The rubber composition of the present invention is suitable as a material for solid tires, heat fillers, solid golf poles, rubber bats, sealing materials, and the like.

[Examples] Next, Examples of the present invention will be explained in more detail.
It goes without saying that the present invention is not limited in any way by this explanation.

Examples 1 to 2 and Comparative Examples 1 to 3 The ingredients shown in Table 1 were mixed with a polybutadiene polymer using a 6-inch roll, cured for a predetermined time using a heated press, and the hardness was measured. The results of comparing the speeds are shown in Table 1. Compared to the comparative example, the crosslinking time was faster and the hardness was also increased.

Examples 3 to 4 and Comparative Examples 4 to 6 The same procedure as in Example 1 was conducted except that curved lead methacrylate was used instead of zinc acrylate. The results are shown in Table 2. Compared to the comparative example, the crosslinking time is faster and the hardness is also increased.

[Effects of the Invention] Further, the rubber composition of the present invention contains a specific polymerizable carboxylic acid metal salt, a specific non-polymerizable carboxylic acid (and/or its metal salt), and a specific phenylene hismaleimide. The combination of these compounds produces an excellent synergistic effect of speeding up crosslinking and increasing the hardness of the crosslinked rubber.

Furthermore, the rubber composition of the present invention is also recognized to be effective in that there is no roll adhesion during kneading and the compounding ingredients are well dispersed.

48 Applicant: Kawaguchi Chemical Industry Co., Ltd. Among agents: 1) Akira PP person! Husband Ryo Hara - −263=

Claims (1)

[Claims] 1. r8) diene rubber (b) metal salt of acrylic acid and/or metal salt of methacrylic acid (■ is 10 to 60 parts by weight per 100 parts by weight of ■). <1 Organic peroxide (■ is ■, ■ is 0.3 to 3 parts by weight based on the total amount of 100 parts by weight.) ・d) (C, 19+ metal oxide and/or metal hydroxide (rpi
) is 1. The amount is 0 to 50 parts by weight per 100 parts by weight of il. ) (f) Huekoshi Nhisumareimito (fj+ / kaif
) has a ball weight ratio of 10/90 to EIO/10. ) A rubber composition obtained by heating and curing a mixture. 2. The rubber composition according to claim 1, which is at least one selected from diene rubber, butadiene rubber, and styrene-butashengo J. 3. The MA composition according to claim 1, wherein the metal of the metal salt of (b) is at least one selected from zinc, magnesium, aluminum and calcium. The oxides are dicumyl peroxide and n-butyl-4,4-his-(t-butylperoxy).
The rubber composition according to claim 1, wherein the rubber composition is at least one yuzu selected from -herylate. 5. The rubber composition according to claim 1, wherein (d) is at least one selected from the group consisting of carphonic acid, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, and naphthenic acid. 6. The rubber composition according to claim 1, wherein the metal of the carboxylic acid metal salt of td> is at least one selected from zinc, calcium, magnesium, aluminum, and sodium. 7. The rubber composition according to claim 1, wherein the metal oxide of .→ is zinc oxide. 8. The rubber composition according to claim 1, wherein the metal hydroxide in ri) is zinc hydroxide. 8. The rubber composition according to claim 8, wherein the phenylene bismaleimide (p) is I-phenylene bismaleimide.