JPS6034582B2 - rubber composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel rubber compositions of ethylene-propylene terpolymers and ethylene-propylene polymers.

Ethylene-propylene terpolymer monosulfate is obtained by vulcanizing a terpolymer of ethylene and propylene into which a non-conjugated diene monomer is introduced as a third component, and is generally
Ethylene-propylene polymer is obtained by vulcanizing a copolymer of ethylene and propylene and is generally called "EPR rubber."

Ethylene-propylene terpolymer diluted products and ethylene-propylene polymer vulcanizates exhibit superior performance in terms of weather resistance, aging resistance, and ozone resistance compared to natural rubber and styrene-butadiene copolymer rubber. It has come to be used in many ways. However, since the vulcanizate does not contain unsaturated bonds or sacrificial groups in the primary mirror, the paint film easily peels off even if paint is applied. For this reason, it is extremely difficult to paint these vulcanizates, and furthermore, they have poor adhesion when adhering to each other or to other materials such as metals and plastics, making it extremely difficult. In order to improve such defects in adhesion or adhesion, many treatment methods have been attempted in the past.

For example, ■ Polishing the surface with a wire brush, sandpaper, etc. ■ Irradiating with ultraviolet rays ■ Immersing in concentrated sulfuric acid ■ Treating with a mixture solution of organic monocarboxylic acid and phosphoric acid ■ Treating with aldehydes ■ Chlorinated polypropylene and Painting with a mixture of ethylenediamine ■ Treating with iodinated isocyanate ■ Oxidizing the surface by exposing it to ozone ■
Methods such as treating with alkyl hypohalite (2) painting with epoxy resin are known. However, with these conventional processing methods, uneven polishing tends to occur in the case of (1), and there are hygiene problems due to the generation of dust.
In the case of , the vulcanized part deteriorates, and in the case of ■, it is dangerous to handle the treatment agent, and in the cases of ■, ■, ■, and ■, the treatment agent is special and the treatment process is complicated; In the cases of , ■, and ■, there were drawbacks such as high equipment costs. Furthermore, even if these treatments are applied, paints, adhesives, etc. and EPD
Adhesion to M or EPR rubber was insufficient. The present inventors conducted various studies on rubber compositions of ethylene-propylene terpolymer and ethylene-propylene polymer, and found that the flexibility and flexibility, which are the characteristics of vulcanized products of these rubber compositions, Without any damage, and
We have developed a new rubber composition that has sufficient adhesion and adhesion to paints, adhesives, etc. on the surface of vulcanizates.

That is, the present invention provides a novel rubber composition made by blending EPDM rubber or EPR rubber with a functional hydrocarbon polymer containing a saturated aliphatic ring. The present invention will be explained in detail below. In the rubber composition of the present invention, a functional hydrocarbon polymer containing a saturated aliphatic ring is blended with an ethylene-propylene turbolimer or an ethylene-propylene polymer. However, the functional hydrocarbon polymer containing a saturated aliphatic ring referred to herein is a polymer as disclosed in Tokkoseki Publication No. 71391/1983.

Particularly preferred are those obtained by hydrogenating a copolymer of a conjugated diene compound and an aromatic compound having a vinyl group. The molecular weight of this hydrocarbon polymer is usually 500-
50,000 castle order, or 1,000 to 30,000. This functional hydrocarbon polymer is produced by heating a functional hydrocarbon polymer having an aromatic ring in the presence of a hydrogenation catalyst.
The functional hydrocarbon polymer having an aromatic ring is obtained by hydrogenation, but the aromatic monomer alone is
Alternatively, it can be obtained by polymerization together with other comonomers according to a conventional method. Typical examples of production methods include a method in which monomers are polymerized until they become a suitable low molecular weight polymer, and a method in which a high molecular weight polymer is oxidatively decomposed. Examples of their manufacturing methods include Tokko No. 37-8190, Tokko No. 38-342, and Tokko No. 42
-22048, Special Publication No. 38-5993, Special Publication No. 1977
No. 114747, Japanese Patent Publication No. 47-136273, and other publications. Examples of the above conjugated gene compounds include 1,3 butadiene, isof. Examples of the vinyl group-containing aromatic compounds include styrene, 1,3-pentadiene, 2,3-dimethylbutadiene, etc.
Vinyltoluene, vinylnaphthalene, phenylbutadiene, methylstyrene, divinylbenzene, chroman,
Examples include indene, cinnamic acid, vinylphenol, and vinylbenzoic acid. These can be used alone or as a mixture. The aromatic monomer content in the above-mentioned functional hydrocarbon polymer having an aromatic ring is 1 to 10% by weight, preferably 5 to 7% by weight based on the polymer.
It is. As a method for hydrogenating this functional hydrocarbon polymer having an aromatic ring, precious metals such as palladium, platinum, rhodium, osmium, and ruthenium are used alone as a catalyst, or carbon, alumina, silica/alumina, diatomite, etc. , barium carbonate, calcium carbonate, etc., and hydrogenation method (Japanese Patent Application Laid-Open No. 51-7638)
(See No. 7). The hydrocarbon polymer containing a saturated aliphatic ring as used in the present invention has a hydroxy group, a carboxy group, etc. as a functional group, and the content of these functional groups is preferably one or more per molecule of the polymer. is 1.5
It is more than one. The rubber composition of the present invention may contain other rubber components, such as natural rubber, styrene-butadiene copolymer rubber, in an amount that does not impair the properties of the ethylene-propylene terpolymer or ethylene-propylene polymer. (SBR), polybutadiene rubber (BR), acrylonitrile butadiene (NBR), polyisoprene (IR), chloroprene rubber (CR), butyl rubber (1
1R) and other resin components, such as polyethylene (PE),
Polyp.

Pyrene (PP), ethylene-vinyl acetate copolymer (EVA), etc. can be contained. The amount is usually no more than 1'a amount of ethylene-propylene terpolymer or ethylene-propylene polymer. The rubber composition of the present invention does not lose the characteristics of EPDM rubber or EPR rubber in its vulcanizate, and also exhibits excellent performance in terms of adhesion and adhesion, as well as light resistance, water resistance, moisture resistance, It exhibits extremely excellent properties such as oxidation resistance, ozone resistance, and heat resistance. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples and Reference Examples, but the present invention is not limited to these Examples.

Production Example 1 of a Functional Hydrocarbon Polymer Having an Aromatic Ring 1.
9. 25 hours of styrene, 70 hours of isopropyl alcohol, and 10 hours of 60% hydrogen oxide solution were charged at room temperature in an argon atmosphere, and the temperature was raised to 90 degrees.

Polymerization was carried out at 9 and 0 for 5 hours, and after cooling, the monomer of the reaction was removed, and the resulting polymer was taken out and dried.

Example 2 Same aircraft as Example 1 above, 1,3-butadiene 64 days,
Styrene 36 times, inpropyl alcohol 70 times and 6 times
Polymerization was carried out at 120° C. for 2 hours using 8 days of 0% hydrogen peroxide solution. Example 3 In the same manner as in Example 1 above, 1,3-butadiene 1009, styrene 1009, inpropyl alcohol 70 and 6
The test was carried out using 0% hydrogen peroxide solution for 5 hours at 90 qo.

Example 4 In the same manner as in Example 1 above, 50 hours of 1,3-ptadiene, 150 hours of styrene, 70 hours of inpropyl alcohol, and 60 hours of inpropyl alcohol were used.
Polymerization was carried out using 109% hydrogen oxide water at 90 qo for 5 hours.

Example 5 Polymerization was carried out in the same manner as in Example 1 above for 1 hour at 12,000 °C using 200 °C of styrene, 70 °C of inpropyl alcohol, and 15 °C of 60% hydrogen peroxide.

Example 6 In the same manner as in Example 1 above, 1,3-butadiene 100
Polymerization was carried out at 90 pm for 5 hours using 70 ml of tisopropyl alcohol and 10 ml of 60% hydrogen peroxide solution.

Production Example 7 of a Functional Hydrocarbon Polymer Having a Saturated Aliphatic Ring 50 parts of the copolymer obtained in Example 1, 50 parts of cyclohexane, and 5 parts of a carbon-supported ruthenium (5%) catalyst were mixed in a volume of 2 parts.
00' autoclave, and after replacing the inside of the system with purified argon gas, hydrogen gas was fed until the amount was 50k9/clump.

The temperature of the contents was raised to 10 psi, and hydrogenation was carried out for 8 hours while supplying hydrogen gas so that the total pressure was maintained at 50 k9/min. After this reaction, hydrogen is removed and the catalyst is removed by a furnace filtration means, and then the generated hydrogenated product is precipitated in methanol,
Dry. Examples 8 and 9 The copolymers obtained in Examples 2 and 3 were each hydrogenated using the same hydrogenation method as in Example 7 to obtain hydrogenated products with high fluidity.

Example 10 The copolymer obtained in Example 4 was hydrogenated using the same hydrogenation method as in Example 7 to obtain a highly viscous hydrogenated product.

Example 11 The styrene homopolymer obtained in Example 5 was hydrogenated in the same manner as in Example 7 to obtain semisolid hydrogenated polystyrene.

Example 12 The polyptadiene polyol obtained in Example 6 was hydrogenated in the same manner as in Example 7 to obtain a waxy hydrogenated polymer.

Example 1 5 parts of the hydrogenated butadiene-styrene copolymer obtained in Example 7, 67.5 parts of EPDMIO, 67.5 parts of carbon black, 35 parts of mineral oil, 5 parts of zinc chloride, 1 part of stearic acid A rubber composition consisting of 20 parts of vulcanization accelerator and 1.5 parts of iodine was vulcanized at 160 qo for 30 minutes.

A urethane prepolymer having NCO at the end (JP-A-50-12 Moth 65) was coated on the rubber material obtained, and after curing at room temperature, a 180 degree peeling machine test was performed. As a result, the peeling strength was 4.5k9/ It was the skin. Examples 2 to 4 Products were prepared in the same manner as in Example 1, except that the hydrogenated butadiene-styrene copolymers obtained in Examples 8, 9, and 10 were used, and the uccinic acid strength was measured. As a result, the skin of Example 2 was 3.6k9/the skin of Example 3 was 5.0k9
/Reduction Example 4 had a value of 3.4k9/enemy.

Example 5 A product was prepared in the same manner as in Example 1, except that the hydrogenated polystyrene obtained in Example 11 was used, and its peeling strength was measured to be 2.5k9/arc.

Example 6 A product was prepared in the same manner as in Example 1 except that the hydrogenated polybutadiene polyol obtained in Example 12 was used, and its peeling strength was measured to be 6.3k9/inhibition.

Table 1 shows the physical properties and peel strength of the rubber materials obtained in Examples 1 to 6.

Table-1

Claims (1)

[Claims] 1. A rubber composition characterized by blending an ethylene-propylene terpolymer or an ethylene-propylene polymer with a functional hydrocarbon polymer containing a saturated aliphatic ring.