JPH01272678A - Adhesive - Google Patents

Abstract

PURPOSE:To obtain an adhesive suitable for adhesion of a non-polar rubber composition of low unsaturated degree, comprising modified material of ethylene-alpha-olefin copolymer-base rubber containing alkenyl aromatic monomer and specific amounts of acid anhydride and dicarboxylic acid. CONSTITUTION:A composition containing a modified material of ethylene-alpha- olefin copolymer-base rubber containing preferably 0.5-7wt.% alkenyl aromatic monomer (e.g., styrene) and 0.1-10 wt.%,. preferably 0.5-5 wt.% acid anhydride (e.g., maleic anhydride) and/or dicarboxylic acid (e.g., maleic acid) as a main component is dissolved in an organic solvent such as pentane to afford an adhesive suitable for cure and adhesion, etc., of a green rubber composition and a cured rubber composition.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a rubber composition and an adhesive suitable for adhering fibers, and more particularly to ethylene-α-olefin copolymer rubber, isobutylene-isoprene The present invention relates to an adhesive suitable for adhering rubber compositions made of low unsaturation nonpolar rubber such as copolymer rubber.

[Conventional technology]

As adhesives for rubber compositions, adhesive compositions mainly composed of polymeric materials containing halogen compounds are widely used, but they do not provide satisfactory adhesive strength to all rubber compositions. However, the present inventors found that ethylene-α containing acid anhydride and/or dicarboxylic acid did not provide sufficient adhesion, especially to rubber compositions made of the above-mentioned low-unsaturation non-polar rubber. - It was discovered that olefin copolymer rubber can be used as an adhesive to provide good adhesion to rubber compositions and fibers made of low unsaturated non-polar rubber, leading to the publication of Japanese Patent Application No. 1982-19282.

[Problem to be solved by the invention]

Under such circumstances, the problem to be solved by the present invention is to provide an adhesive made of a modified ethylene-α-olefin copolymer rubber having excellent adhesion to rubber compositions and the like.

[Means to solve the problem]

That is, the present invention provides alkenyl aromatic monoclaws and 0.1 to 0.1 to
The present invention relates to an adhesive characterized in that ξ is made of an ethylene-α-onfin copolymer rubber containing 10 weight percent of an acid anhydride and/or dicarboxylic acid as a main component. Furthermore, the present invention relates to an adhesive characterized in that the copolymer rubber is dissolved in an organic solvent.

The present invention will be explained in detail below.

<1) In the present invention, the ethylene-α-olefin copolymer rubber refers to ethylene-olefin copolymer and ethylene-α-osifine-nonconjugated diene copolymer, and as α-olefin 2 is preferably a carbon number of 8 to 10, and 2 is propylene, 1-
Examples include butene, 1-pentene, 1-hexene, and the like.

Examples of non-conjugated dienes include dicyclobentadiene, ethylidene norbornene, 1,4-hexadiene,
Examples include methyltetrahydroindene and methylnorbornene.

(2) The acid anhydride of the present invention refers to 71 main acid anhydride,
Examples include citraconic anhydride, nadic anhydride, etc., and dicarboxylic acids include maleic acid, fumaric acid, itaconic acid,
Examples include citraconic acid and nadic acid.

Furthermore, in the present invention, the content of acid anhydride and/or dicarboxylic acid is limited to 0.1 to 10% by weight, because below this range, the adhesive strength is low, and above this range, the adhesive strength is large. This is because no significant improvement effect is expected.

A preferred range is 2 to 8 weight percent Oo, and a more preferred range is 0.6 to 6 iitffi percent.

(8) Examples of the alkenyl aromatic monomer of the present invention include styrene, 0-methylstyrene, p-methylstyrene, m-methylstyrene, and α-methylstyrene. The content of aromatic monomer is 0.5~γil
I would like a cent.

The modified ethylene-α·-olefin copolymer rubber thus obtained can be used as an adhesive without being dissolved in a solvent.

Another embodiment of the present invention is an adhesive prepared by dissolving the modified ethylene-α-olefin copolymer rubber in an organic solvent.

This adhesive exhibits excellent adhesion to rubber compositions, particularly to low unsaturation nonpolar rubber compositions.

(4) The organic solvent in the present invention refers to aliphatic, aromatic, and aliphatic solvents for halogen-containing compounds, and specifically includes pentane, hexane, cyclohexane, benzene, toluene, xylene, ethylbenzene, ethyltoluene, cumene, and diethylbenzene. , chloroform, and tetrachloride's. The dissolved concentration of the ethylene-α-olefin copolymer rubber containing acid anhydride and/or dicarboxylic acid is 6 to
50! The optimum concentration is selected within the range of 1% according to the molecular weight of the ethylene-α-olefin copolymer rubber and the method of applying the adhesive.

(5) In the present invention, reinforcing agents, fillers, softeners, adhesives, etc. known in the adhesive industry or rubber industry can be added as necessary.

The adhesive of the present invention exhibits excellent adhesion to rubber compositions, particularly compositions of low unsaturation nonpolar rubbers such as ethylene-α-olefin copolymer rubber and isobutylene-isoprene rubber. Specifically, vulcanization adhesion between an unvulcanized rubber composition and a vulcanized rubber composition, adhesion between vulcanized rubber compositions, and vulcanization adhesion between an unvulcanized rubber composition and natural fibers and/or synthetic fibers. , exhibits excellent adhesion between vulcanized rubber compositions and delicate natural and/or synthetic fiber nonwoven fabrics.

Furthermore, the adhesive composition of the present invention can be applied to bonding natural fibers and/or synthetic fibers.

A more specific explanation will be given below according to examples.

〔Example〕

Examples 1-6 Comparative Examples 1-4 Table 1 shows the composition of the adhesive used in Examples and Comparative Examples.

After adding additives as necessary to the maleic anhydride-containing ethylene-α-olefin copolymer rubber using a roll, Table 1
A predetermined amount of the organic solvent shown in 1 was added, and the mixture was heated at 60° C. for 8 hours to dissolve in the C1 organic solvent to obtain adhesives A and C. Adhesive B was obtained by leaving a maleic anhydride-containing ethylene-α-olefin copolymer rubber in a constant temperature and humidity bath at 60° C. and 80% humidity for 8 hours, and then dissolving it in an organic solvent under the above conditions.

For the IT solution, the ethylene-olefin copolymer was similarly dissolved in an organic solvent.

Table 2 shows the composition of the rubber adherend. Compound A in Table 2 is B
The mixture was kneaded using an R-type Banbury, and compounding agent B was added to this kneaded product using an 8-inch diameter roll, and the resulting unvulcanized rubber composition was press-vulcanized under the vulcanization conditions shown in Table 2. A vulcanized sheet measuring 150 x 150 x 2 m was obtained. A strip-shaped test piece of 20wXi50m was produced from this sheet using a punching blade.

The fiber adherend was prepared by cutting a woven fabric into strips of 4 to 200 m in size. Adhesives A and D shown in Table 1 are uniformly applied to a strip-shaped test piece of a vulcanized rubber adherend using a glass rod, and in the case of two vulcanized rubber adherends, the adhesive is left for 80 minutes after application. The adhesive-coated surfaces of the test pieces were bonded together. Vulcanized rubber adherend and l1JAIl
i The adherends were bonded together immediately after applying the adhesive.

After that, 2~ hand rollers are made to reciprocate 8 times and brought into close contact.
It was cured under no load under the curing conditions shown in Table 8.

In the case of vulcanized rubber adherends and fiber adherends, after curing, cut the protruding fiber adherends with scissors to the same size as the vulcanized rubber strip test piece. The adhesive strength was measured by performing a 180° peel test at a tensile speed of 59 m/min in accordance with JIS K 611.

The results are shown in Table 8.

Examples 7 to 11, Comparative Examples 5 to 7 The unvulcanized rubber composition of EPDM composition A shown in Table 2 was prepared into a 2-inch thick sheet using a bin roll. It was cut into a size of 150 x 150 cm and used as a test piece. The adhesives in Table 1 were applied to specimens of unvulcanized rubber compositions. In the case of an unvulcanized rubber composition adherend - a vulcanized rubber composition adherend, it was applied and left for 80 minutes, and then an adhesive was applied and left for the same time. A rubber composition sheet was pasted together. Unvulcanized rubber composition adherend - In the case of a fiber adherend, immediately after application, 150X
Woven fabrics with a size of 150 cm were pasted together. In both cases, a hand roller with two noodles was rolled back and forth 8 times to bring them into close contact. 81kf/c
Vulcanization was carried out at 160° C. for 80 minutes in IA pressurized air. It was punched out into a strip of 20 x 150 m using a punching blade. This strip-shaped test piece was tested according to JIS K 6801.
A 180° peel test was conducted at zero tensile speeds to measure the adhesive strength. The results are shown in Table 4.

Examples 12 to 14 Comparative Examples 8 to 9 Cut the sown cloth to a size of 150 x 150 m, apply the adhesive shown in Table 1 evenly with a glass rod, and immediately paste 150 x 150 pieces of uncoated woven fabric. In addition, curing was performed under the curing conditions shown in Table 5. 20X15Q using a punching blade
A strip-shaped test piece of m was prepared.

180” at a tensile speed of 59 m for this strip specimen.
A peel test was conducted to measure the adhesive strength. Maze 5 ki'hi & cough 1-, Ikura ♀ round-? B=1° [Effects of the Invention] As described above, according to the present invention, it is possible to provide an adhesive having excellent adhesive properties and suitable for EPDM, lia maintenance, and the like.

Claims (2)

[Claims] (1) The main component is a modified ethylene-α-olefin copolymer rubber containing an alkenyl aromatic monomer and 0.1 to 10 weight percent of an acid anhydride and/or dicarboxylic acid. glue. (2) An adhesive characterized in that the modified ethylene-α-olefin copolymer rubber according to claim 1 is dissolved in an organic solvent.