JP2014162823A - Rubber bonded structure, production method of the same, and adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite molding formed of firmly bonded rubber moldings, which often lack sufficient adhesive strength in conventional arts, by having a layer formed by crosslinking an adhesive.SOLUTION: The rubber bonded structure comprises an adherend (1) which is a rubber molding, a layer formed by crosslinking an adhesive (X), and an adherend (2) which is a molding of rubber or another material, which are in contact. The adhesive (X) comprises an ethylene-α-olefin-polyene copolymer (A) having viscosity of 1 Pa s or higher but 5000 Pa s or lower at 25°C and at least one crosslinking agent (B) selected from the group consisting of the following (B-1), (B-2), and (B-3): (B-1) organic peroxides and allyl compound-based crosslinking auxiliaries; (B-2) sulfur-based compounds; and (B-3) SiH group-containing compounds.

Description

  The present invention relates to an adhesive body obtained by bonding rubber molded bodies, a method for producing the same, and an adhesive. Specifically, the present invention satisfactorily adheres an adhesive body obtained by adhering a rubber molded article formed into a desired shape such as a sheet using a liquid adhesive, a manufacturing method thereof, and nonpolar rubber. It relates to a liquid adhesive.

  Adhesion between rubber moldings, especially non-polar rubber moldings such as ethylene / propylene / diene rubber (EPDM), and moldings of other materials such as metals and plastics or similar rubber moldings It is known to be difficult.

  As a method for producing an adhesive body of a rubber molded body, for example, a method is known in which a crosslinked rubber sheet and an uncrosslinked rubber sheet are bonded together and bonded by crosslinking. However, this method has problems that it is necessary to heat the entire molded product so that not only the bonded portion but also the entire uncrosslinked rubber is crosslinked, and that it is difficult to apply to the manufacture of adherends with complicated shapes. It was.

For this reason, pressure-sensitive adhesives and the like have been mainly used in the production of an adhesive body of a rubber molded body.
As a method for improving the adhesiveness of a rubber molded body, a method for improving the adhesion by modifying the surface by sequentially treating the surface of a vulcanized rubber molded body with a halogenating agent and a polyfunctional amine-containing organic compound. (Refer to Patent Document 1), a method of applying a phenolic resin-based undercoat adhesive and a topcoat adhesive containing chlorinated polyethylene to a metal surface (Patent Document 2), latex and maleation when bonding rubber and metal A method of adhering a reinforcing fiber material to ethylene / propylene / diene rubber using an adhesive composition comprising an aqueous solution of a half ester of a liquid polybutadiene resin has been proposed (Patent Document 3).

  Further, as an adhesive for adhering a rubber molded body, chloroprene containing a tackifier resin, a metal oxide or a metal hydroxide, a chloroprene (co) polymer, and an organic solvent, and having adhesiveness and thixotropic properties A rubber adhesive (Cited Document 4), a liquid rubber adhesive composition (Cited Document 5) containing a surface-treated inorganic filler, liquid rubber and a curing agent have been proposed.

  However, the surface treatment of the adherend has a problem that the efficiency of the adhesion process is increased and the efficiency is poor, and when an adhesive mainly composed of a rubber molded body to be bonded and an incompatible structure is used. There was a problem that the interfacial peel strength was low and the durability was poor. In addition, the solvent-type adhesive needs to volatilize the solvent at the time of use, and the use of a non-solvent type adhesive is desired in view of environmental concerns and health hazards to the user.

  For this reason, the advent of a non-solvent type adhesive and a rubber bonded body in which the cured adhesive and the rubber molded article to be bonded are firmly integrated has been demanded.

JP-T-2002-539279 Japanese Patent Laid-Open No. 2004-27068 JP 2005-519182 gazette JP-A-10-212465 JP-A-56-90868

  The present invention relates to a rubber bonded body in which a rubber molded body and an adherend, in particular, a crosslinked rubber molded body and an adherend are firmly bonded with a non-solvent adhesive without performing a prior surface treatment, and It is an object of the present invention to provide a non-solvent type adhesive in which an adhesive after curing and a rubber molded article as an adherend are firmly integrated.

The rubber bonded body of the present invention is
A rubber bonded body formed by contacting an adherend (1) which is a rubber molded body, a layer formed by crosslinking the adhesive (X), and an adherend (2) which is a molded body made of rubber or other materials. Because
The adhesive (X) has an ethylene / α-olefin / polyene copolymer (A) having a viscosity at 25 ° C. of 1 Pa · s or more and less than 5,000 Pa · s, and the following (B-1 ), (B-2) and (B-3), and at least one crosslinking agent (B) selected from the group consisting of (B-3);
(B-1) Organic peroxide and allyl compound-based crosslinking aid,
(B-2) a sulfur compound,
(B-3) SiH group-containing compound.

  In such a rubber adhesive of the present invention, the polyene of the ethylene / α-olefin / polyene copolymer (A) is 1,3-butadiene, isoprene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5 It is preferably at least one selected from -vinyl-2-norbornene.

  In the rubber bonded body of the present invention, the crosslinking agent (B) is preferably (B-1) an organic peroxide and an allyl compound-based crosslinking aid. In addition, the crosslinking agent (B) is represented by the organic peroxide described in the following general formula (a) and / or the following general formula (b), and the following formula (c) and / or the following formula (d). It is more preferable to contain an allyl compound-based crosslinking aid.

X ¹ —O—O—X ² —O—O—X ³ (a)
(In formula (a), X ¹ , X ² and X ³ each independently represents an organic group having 4 or more carbon atoms)
Y ¹ —O—O—Y ² (b)
(In formula (b), Y ₁ and Y ₂ each independently represents an organic group having 4 or more carbon atoms)

本発明のゴム接着体では、前記エチレン・α−オレフィン・ポリエン共重合体（Ａ）が、135℃のデカリン溶液で測定した極限粘度[η]が０．０１〜０．５０ｄｌ／ｇの範囲であることが好ましい。

In the rubber adhesive of the present invention, the ethylene / α-olefin / polyene copolymer (A) has an intrinsic viscosity [η] measured with a decalin solution at 135 ° C. in the range of 0.01 to 0.50 dl / g. Preferably there is.

  In the rubber bonded body of the present invention, the ethylene / α-olefin / polyene copolymer (A) is preferably an ethylene / α-olefin / non-conjugated polyene, and preferably an ethylene / propylene / non-conjugated polyene. More preferred is ethylene / propylene / 5-vinyl-2-norbornene.

In the rubber bonded body of the present invention, it is preferable that the adhesive (X) does not substantially contain a solvent.
In the rubber bonded body of the present invention, at least one of the adherend (1) and the adherend (2) is a crosslinked rubber obtained by using at least one selected from sulfur and peroxide as a crosslinking agent. A molded body is preferable, and the adherend (1) and the adherend (2) are more preferably sheet-like crosslinked rubber molded bodies.

The method for producing a rubber bonded body of the present invention includes:
On the adhesion surface of the adherend (1) which is a rubber molded body and / or the adhesion surface of the adherend (2) which is a molded body made of rubber or other material,
An ethylene / α-olefin / polyene copolymer (A) having a viscosity at 25 ° C. of 1 Pa · s or more and less than 5,000 Pa · s, the following (B-1), (B-2) and Applying an adhesive (X) containing at least one crosslinking agent (B) selected from the group consisting of (B-3);
Bonding the adhesion surfaces of the adherend (1) and the adherend (2) through the applied adhesive (X);
A step of cross-linking the adhesive (X);
(B-1) Organic peroxide and allyl compound-based crosslinking aid,
(B-2) a sulfur compound,
(B-3) SiH group-containing compound.

The adhesive (X) for producing a rubber bonded body of the present invention is
An ethylene / α-olefin / polyene copolymer (A) having a viscosity at 25 ° C. of 1 Pa · s or more and less than 5,000 Pa · s;
At least one crosslinking agent (B) selected from the group consisting of the following (B-1), (B-2) and (B-3)
Is characterized by containing;
(B-1) Organic peroxide and allyl compound-based crosslinking aid,
(B-2) a sulfur compound,
(B-3) SiH group-containing compound.

  In such an adhesive (X) for producing a rubber bonded body of the present invention, the polyene of the ethylene / α-olefin / polyene copolymer (A) is 1,3-butadiene, isoprene, dicyclopentadiene, 5- It is preferably at least one selected from ethylidene-2-norbornene and 5-vinyl-2-norbornene.

  In the adhesive (X) for producing a rubber bonded body according to the present invention, the crosslinking agent (B) is preferably (B-1) an organic peroxide and an allyl compound-based crosslinking aid. In addition, the crosslinking agent (B) is represented by the organic peroxide described in the following general formula (a) and / or the following general formula (b), and the following formula (c) and / or the following formula (d). It is more preferable to contain an allyl compound-based crosslinking aid.

X ¹ —O—O—X ² —O—O—X ³ (a)
(In formula (a), X ¹ , X ² and X ³ each independently represents an organic group having 4 or more carbon atoms)
Y ¹ —O—O—Y ² (b)
(In formula (b), Y ₁ and Y ₂ each independently represents an organic group having 4 or more carbon atoms)

本発明のゴム接着体製造用接着剤（Ｘ）では、前記エチレン・α−オレフィン・ポリエン共重合体（Ａ）が、135℃のデカリン溶液で測定した極限粘度[η]が０．０１〜０．５０ｄｌ／ｇの範囲であることが好ましい。

In the adhesive (X) for producing a rubber bonded body according to the present invention, the ethylene / α-olefin / polyene copolymer (A) has an intrinsic viscosity [η] measured by a decalin solution at 135 ° C. of 0.01 to 0. It is preferably in the range of .50 dl / g.

  In the adhesive (X) for producing a rubber bonded body according to the present invention, the ethylene / α-olefin / polyene copolymer (A) is preferably an ethylene / α-olefin / non-conjugated polyene. It is more preferably a conjugated polyene, and further preferably ethylene / propylene / 5-vinyl-2-norbornene.

It is preferable that the adhesive (X) for producing a rubber bonded body of the present invention does not substantially contain a solvent.
The adhesive (X) for producing a rubber bonded body of the present invention can be suitably used for an application for bonding a crosslinked rubber molded body.

  The rubber bonded body of the present invention has a layer formed by crosslinking a specific adhesive, so that a rubber molded body that has conventionally been difficult to obtain sufficient adhesive strength is firmly bonded. According to the present invention, a composite molded body obtained by bonding a rubber molded body such as a crosslinked rubber molded body can be provided.

  According to the method for producing a rubber bonded body of the present invention, by using an adhesive having a specific viscosity that does not need to contain a solvent substantially, no pretreatment such as surface treatment is required, and the adhesive is directly bonded to the surface. A rubber molded body such as a crosslinked rubber molded body, which has been difficult to obtain a sufficient adhesive strength in the past, can be firmly bonded without generating a volatile solvent. In such a manufacturing method, it is not necessary to collect the volatilized solvent, the process is simple, the environment is low in load, and unlike the case of bonding with an adhesive sheet or the like, even on an adherend having a complicated shape. An adhesive can be easily applied, and a rubber bonded body that is a composite in which adherends are firmly bonded can be easily manufactured.

  The adhesive according to the present invention is suitable for adhesion of a rubber molded body, and has a specific viscosity, so that it can be used by being applied to an adherend even if it contains substantially no solvent. -A crosslinked body can be formed by a simple operation such as compression, and a rubber molded body or the like can be firmly bonded. Moreover, since it does not need to contain a solvent substantially, a volatile solvent does not generate | occur | produce at the time of use, and it has the advantage that there are few burdens on a human body and an environment.

Hereinafter, the present invention will be specifically described.
The rubber bonded body according to the present invention includes an adherend (1) which is a rubber molded body, a layer obtained by crosslinking the adhesive (X), and an adherend (which is a molded body made of rubber or other material). 2).

  In the method for producing a rubber bonded body according to the present invention, the bonding surface of the bonded body (1) which is a rubber molded body and / or the bonded body (2) which is a molded body made of rubber or other material. A step of applying the adhesive (X) to the bonding surface, a step of bonding the bonding surfaces of the adherend (1) and the adherend (2) via the applied adhesive (X), and an adhesive; A step of crosslinking (X).

<Adhesive (X)>
First, the adhesive (X) according to the present invention will be described.
The adhesive (X) according to the present invention includes an ethylene / α-olefin / polyene copolymer (A) and a crosslinking agent (B).

Ethylene / α-olefin / polyene copolymer (A)
The adhesive (X) according to the present invention contains an ethylene / α-olefin / polyene copolymer (A) as a main component.

  The ethylene / α-olefin / polyene copolymer (A) constituting the adhesive (X) according to the present invention includes a structural unit [i] derived from ethylene and a structural unit [ii] derived from an α-olefin. And a structural unit [iii] derived from polyene.

(Α-olefin)
The structural unit [ii] constituting the ethylene / α-olefin / polyene copolymer (A) according to the present invention is a structural unit derived from an α-olefin, preferably an α having 3 to 20 carbon atoms. -Structural units derived from olefins.

Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-nonene, Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl- Examples include 1-dodecene and 12-ethyl-1-tetradecene. Among these, α-olefins having 3 to 10 carbon atoms are preferable, propylene, 1-butene, 1-hexene, 1-octene, and the like are more preferable, and propylene is particularly preferable.
These α-olefins are used alone or in combination of two or more.

(Polyene)
The structural unit [iii] constituting the ethylene / α-olefin / polyene copolymer (A) according to the present invention is a structural unit derived from polyene.

  As the polyene, hydrocarbons having two or more double bonds, such as dienes and trienes, can be used without particular limitation. The polyenes may be aliphatic or alicyclic polyenes, and are non-conjugated polyenes. Or a conjugated polyene. The ethylene / α-olefin / polyene copolymer copolymer (A) according to the present invention is not limited to structural isomers such as trans isomers and cis isomers as long as the effects of the present invention are exhibited.

  Non-conjugated polyenes include, for example, 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl- Chain non-conjugated dienes such as 1,4-hexadiene, 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2- Cyclic non-conjugated dienes such as norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, dicyclopentadiene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene And trienes such as 2-propenyl-2,2-norbornadiene.

  Examples of the non-conjugated polyene include a terminal vinyl group-containing norbornene compound, and examples thereof include compounds represented by the following formula [I] or [II].

（式［Ｉ］中、ｎは０ないし１０の整数であり、Ｒ¹は水素原子または炭素原子数１〜１０のアルキル基であり、Ｒ²は水素原子または炭素原子１〜５のアルキル基である）

(In the formula [I], n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. is there)

（式［II］中、Ｒ³は水素原子または炭素原子１〜１０のアルキル基である）

(In the formula [II], R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms)

  Examples of such a terminal vinyl group-containing norbornene compound include 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, and 5- (3-butenyl)- 2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) ) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- 2-Methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexesyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- ( 1,2,3-trimethyl-4-pentenyl) -2-norbornene and the like. Among these, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) ) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (7-octenyl)- 2-norbornene is preferred.

  Examples of the conjugated polyene include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, and 2-hexyl-1. , 3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-1,3-butadiene, 2-methyl-1,3-hexadiene, 2, -Methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-dimethyl-1,3-octadiene, 2,3-dimethyl-1 1,3-decadiene and the like, 1,2-butadiene, 1,3-butadiene, isoprene and the like are preferable, and 1,3-butadiene and isoprene, which have better copolymerization, are particularly preferable.

  Among these polyenes, 1,3-butadiene, isoprene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene are preferable, and the polyene contains one or more of these. Is preferred. It is also preferred that the polyene is a non-conjugated polyene.

These polyenes can be used alone or in combination of two or more.
When polyene is used in combination with a terminal vinyl group-containing norbornene compound and another polyene as the polyene to form an ethylene / α-olefin / polyene copolymer (A), the polyene component contains a terminal vinyl group Other polyenes are usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, particularly preferably 10 mol% or less with respect to 100 mol% of the norbornene compound. is there.

  Among such ethylene / α-olefin / polyene copolymers (A), the polyene of the ethylene / α-olefin / polyene copolymer (A) is not particularly limited. It is preferably at least one selected from 3-butadiene, isoprene, dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene, and may be ethylene / α-olefin / non-conjugated polyene. preferable. The ethylene / α-olefin / polyene copolymer (A) is preferably ethylene / propylene / non-conjugated polyene, and more preferably ethylene / propylene / 5-vinyl-2-norbornene.

  In the present invention, the ethylene / α-olefin / polyene copolymer (A) preferably used is a molar ratio of a structural unit [i] derived from ethylene and a structural unit [ii] derived from an α-olefin ( [I] / [ii]) is in the range of 35/65 to 95/5, preferably 40/60 to 90/10, more preferably 45/55 to 85/15. When the molar ratio is within the above range, an adhesive having excellent light transmittance (light transmittance) and having little influence on the color tone of the obtained rubber adhesive even when the adherend has transparency or little coloration. This is preferable.

Here, the composition of the ethylene / α-olefin / polyene copolymer (A) can be measured using, for example, ¹³ C-NMR.
In addition, the ethylene content of the ethylene / α-olefin / polyene copolymer (A) according to the present invention is preferably 51 to 88 mol%, more preferably 55 to 75 mol in 100 mol% of the copolymer (A). Mol%. If the ethylene content is too low, the low temperature characteristics of the copolymer (A) may be deteriorated, and if it is too high, the resin is likely to be solid due to crystallization, and workability may be deteriorated.

  Further, the polyene content in the ethylene / α-olefin / polyene copolymer (A) is not particularly limited as long as the iodine value described later is satisfied, but preferably 0 in 100 mol% of the copolymer (A). 0.05 to 8 mol%, more preferably 0.1 to 6 mol%, still more preferably 0.5 to 5 mol%. If the polyene content is too low, the cross-linking speed becomes slow and the cross-linking density also becomes low, which may deteriorate the workability during bonding. If the polyene content is too high, a branched structure based on the polyene part will occur. Threading and viscosity increase may occur and workability may deteriorate.

  The ethylene / α-olefin / polyene copolymer (A) according to the present invention has an iodine value in the range of 0.5 to 50 g / 100 g, preferably 1 to 40 g / 100 g, more preferably 5 to 30 g / 100 g. is there. It is desirable for the iodine value to be in the above range since an adhesive (X) having an excellent crosslinking rate can be obtained. An iodine value exceeding 50 is not preferable because it is disadvantageous in terms of cost.

  The ethylene / α-olefin / polyene copolymer (A) according to the present invention has a viscosity at 25 ° C. of 1 Pa · S or more and less than 5000 Pa · S, preferably 3 Pa · S or more, 2000 Pa · S. The range is less than 1000 Pa · S, more preferably 5 Pa · S or more and less than 1000 Pa · S. When the viscosity of the ethylene / α-olefin / polyene copolymer (A) is in such a range, the adhesive (X) can be handled in a liquid state, and the adhesive (X) to the adherend surface of the adherend. This is preferable because the coating property of the resin becomes good. In addition, it is preferable that the adhesive (X) is in a liquid state because the adhesive (X) easily spreads to the adherend surface serving as an adhesive surface and the adhesiveness is improved.

  The ethylene / α-olefin / polyene copolymer (A) according to the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.01 to 0.50 dl / g, preferably 0.01. It is desirable to be in the range of ˜0.40 dl / g, more preferably 0.03 to 0.35 dl / g.

When the intrinsic viscosity [η] is within the above range, an adhesive (X) exhibiting a liquid state, good fluidity and excellent coating properties can be obtained.
If the intrinsic viscosity [η] is too low, the cohesive force as a polymer may not be obtained, and the adhesive strength may decrease. If it is too high, the liquid viscosity becomes too high, and the workability applied to the adherend surface of the adherend is reduced. There is a problem of doing.

  Moreover, when it exceeds the range of the intrinsic viscosity [η], it is necessary to add a large amount of a plasticizer or a solvent in order to use it in a liquid state, and the adhesiveness may be deteriorated. In addition, it may be necessary to volatilize the solvent, a solvent removal step may be required, and there may be a concern about environmental and human effects.

  In the present invention, considering the kind and amount of components other than the copolymer (A) constituting the adhesive (X), and considering the desired application performance of the adhesive (X), an appropriate intrinsic viscosity [ An ethylene / α-olefin / polyene copolymer (A) having η] can be selected and used.

The ethylene / α-olefin / polyene copolymer (A) according to the present invention is preferably liquid at normal temperature.
Further, the molecular weight (Mn) of the ethylene / α-olefin / polyene copolymer (A) according to the present invention measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 100 to 10,000. More preferably, it is 500-5,000. The molecular weight distribution (Mw / Mn) is not particularly limited, but is preferably 10 or less, more preferably 5 or less. When the molecular weight distribution (Mw / Mn) is within the above range, an adhesive (X) having little thixotropy and excellent coating properties can be obtained.

Production Method of Ethylene / α-Olefin / Polyene Copolymer (A) The ethylene / α-olefin / polyene copolymer (A) according to the present invention comprises ethylene and the α-olefin and polyene described above by a known method. It can be produced by copolymerization. For example, “Polymer production process (Industry Research Committee, p. 309-330), or JP-A-9-71617, JP-A-9-71618, It can be prepared by a conventionally known method as described in JP-A-9-208615, JP-A-10-67823, JP-A-10-67824, JP-A-10-110054 and the like. More specifically, although not particularly limited, the ethylene / α-olefin / polyene copolymer (A) according to the present invention includes, for example, It can be manufactured by the following manufacturing method.

  The ethylene / α-olefin / polyene copolymer (A) according to the present invention is represented by the following general formula (III-a) or vanadium compound represented by the following general formula (III-b) and the following general formula (IV). In the presence of a catalyst containing an organoaluminum compound as a main component, a polymerization temperature of 30 to 60 ° C., particularly preferably 30 to 59 ° C., a polymerization pressure of 0.4 to 5.0 MPa, particularly preferably 0.5 to 4. Produced suitably by random copolymerization of ethylene, α-olefin, and polyene under the conditions of 0 MPa, molar ratio of polyene and ethylene supplied (polyene / ethylene) of 0.01 to 0.2. Can do. The copolymerization is preferably carried out in a hydrocarbon medium.

[Vanadium compounds]
The vanadium compound that can be used for the production of the ethylene / α-olefin / polyene copolymer (A) according to the present invention is a component that is soluble in the hydrocarbon medium of the polymerization reaction system, specifically,
VO (OR) _a X _b (III-a) or V (OR) _c X _d (III-b)
(Wherein R is a hydrocarbon group, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4)
The vanadium compound represented by these, or these electron donor adducts can be mentioned as a representative example.

More specifically, VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (On-C _{4 H 9) Cl 2, VO} (OC 2 H 5) 3, VOBr 3, VCl 4, VOCl 3, VO (O-n-C 4 H 9) 3, illustrates and VCl ₃ · 2OC ₆ H ₁₂ OH be able to.

  Further, as the catalyst used in the copolymerization, a so-called metallocene catalyst such as a metallocene catalyst described in JP-A-9-40586 may be used. Further, as the catalyst used in the above copolymerization, a nonmetallocene catalyst such as a transition metal complex catalyst described in WO2006 / 121086 can also be used.

[Organic aluminum compound]
Examples of the organoaluminum compound that can be suitably used for the production of the ethylene / α-olefin / polyene copolymer (A) according to the present invention include compounds represented by the following general formula (IV).

_{R 'm AlX' 3-m} ··· (IV)
(In Formula (IV), R ′ is a hydrocarbon group, X ′ is a halogen atom, and m is 1 to 3.)

Specific examples of the organoaluminum compound according to the present invention include trialkylaluminums such as triethylaluminum, tributylaluminum, and triisopropylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum sesquiethoxide, Alkylaluminum sesquialkoxides such as butylaluminum sesquibutoxide; partially alkoxylated alkylaluminums having an average composition represented by R ¹ _0.5 Al (OR ¹ ) _0.5 ; diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, etc. Dialkylaluminum halides; ethylaluminum sesquichloride, butylaluminum sesquik Alkyl aluminum sesquihalides such as Lido, ethylaluminum sesquibromide, partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; diethylaluminum hydride, dibutylaluminum hydride Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as dialkylaluminum hydride, ethylaluminum dihydride, propylaluminum dihydride, etc .; moieties such as ethylaluminum ethoxychloride, butylaluminum butoxycyclide, ethylaluminum ethoxybromide Alkoxylated and halogenated alkylaluminum Can be mentioned.

In the present invention, among the vanadium compound (III-a), the soluble vanadium compound represented by VOCl ₃ and the organoaluminum compound (IV), Al (OC ₂ H ₅ ) ₂ Cl / Al ₂ (OC ₂ When a blend of H ₅ ) ₃ Cl ₃ (blend ratio is 1/5 or more) is used as a catalyst component, the insoluble matter after Soxhlet extraction (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) is 1 % Or less is preferable because an ethylene / α-olefin / polyene copolymer (A) is obtained.
As the catalyst used in the copolymerization, a so-called metallocene catalyst, for example, a metallocene catalyst described in JP-A-9-40586 may be used.

Cross-linking agent (B)
The adhesive (X) according to the present invention contains a crosslinking agent (B) together with the above-described ethylene / α-olefin / polyene copolymer (A).

As the crosslinking agent (B), (B-1) an organic peroxide and an allyl compound-based crosslinking aid,
Examples thereof include at least one selected from the group consisting of (B-2) a sulfur compound and (B-3) a SiH group-containing compound.

(B-1) Organic peroxide and allyl compound-based crosslinking aid (organic peroxide)
As the organic oxide, organic peroxides usually used as a crosslinking agent in EPR and EPDM can be used without particular limitation. For example, the organic peroxide is represented by the following general formula (a) and the following general formula (b). An organic peroxide is mentioned.

X ¹ —O—O—X ² —O—O—X ³ (a)
(In formula (a), X ¹ , X ² and X ³ each independently represents an organic group having 4 or more carbon atoms)
Y ¹ —O—O—Y ² (b)
(In formula (b), Y ₁ and Y ₂ each independently represents an organic group having 4 or more carbon atoms)

  Specific examples of such organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5 -Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5 -Trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, Diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-2,5 amyl peroxide, t-butylhydro Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2 , 5- Mono (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene and other dialkyl peroxides; t-butylperoxyacetate, t-butylperoxy Isobutyrate, t-butyl peroxybivalate, t-butyl peroxymaleic acid, t-butyl pero Peroxyesters such as cineeodecanoate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, 1,1-bis-t-butylperoxy-3,3,5-tri-methylcyclohexane, Examples thereof include ketone peroxides such as dicyclohexanone peroxide, and mixtures thereof. Among these, organic peroxides having a temperature giving a half-life of 1 minute in the range of 130 ° C. to 200 ° C. are preferable.

  Among these, dicumyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2 are preferred in terms of reactivity, odor, and scorch stability. Bifunctional organic peroxides such as 1,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (-(tertbutylperoxyisopropyl) benzene and the like are particularly preferable. -Dimethyl-2,5-di- (tert-butylperoxy) hexane and dicumyl peroxide are more preferable.

These organic peroxides may be used alone or in combination of two or more.
The organic peroxide is usually used in a proportion of 0.001 to 0.05 mol, preferably 0.001 to 0.03 mol, per 100 g of the ethylene / α-olefin / polyene copolymer (A). It is desirable to determine the optimum amount as appropriate according to the required physical property value.

  In this invention, when a crosslinking agent (B) contains an organic peroxide, in addition to this, an allyl compound type crosslinking adjuvant is included. Since the adhesive (X) obtained by this shows the outstanding adhesive strength, it is preferable.

(Allyl compound crosslinking aid)
As an allyl compound-based crosslinking aid used as a crosslinking agent (B-1) component together with an organic peroxide, a compound having an allyl group and acting as a crosslinking aid can be used without limitation. For example, diallyl phthalate And allyl compounds such as triallyl isocyanurate and trimethallyl isocyanurate.

  Among these, a crosslinking aid (triallyl isocyanurate) represented by the following formula (c) and / or a crosslinking aid (trimethallyl isocyanurate) represented by the following formula (d) is preferably used.

有機過酸化物とともに架橋剤（Ｂ−１）成分として用いられるアリル化合物系架橋助剤としては有機過酸化物と併用するこれらの架橋助剤は、1種単独で用いてもよく、2種以上組み合わせて用いてもよい。

As the allyl compound-based crosslinking aid used as the crosslinking agent (B-1) component together with the organic peroxide, these crosslinking aids used in combination with the organic peroxide may be used alone or in combination of two or more. You may use it in combination.

Such an allyl compound-based crosslinking aid is usually used at a ratio of 0.5 to 2 mol, preferably an equivalent mol, with respect to 1 mol of the organic peroxide used.
The crosslinking agent (B-1) may contain a crosslinking aid other than the allyl compound-based crosslinking aid in addition to the allyl compound-based crosslinking aid. Examples of such crosslinking aids include sulfur; quinone dioxime compounds such as P-quinone dioxime; acrylic compounds such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; other maleimide compounds, divinylbenzene ( DVB) and the like.
The crosslinking agent (B-1) includes an organic peroxide represented by the general formula (a) and / or the general formula (b) and an allyl represented by the above formula (c) and / or (d). It is particularly preferable to include a compound-based crosslinking aid.

-(B-2) Sulfur-based compound Examples of the sulfur-based compound include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate. Among these, sulfur is preferable.
A sulfur type compound is 0.1-10 mass parts normally with respect to 100 mass parts of ethylene * alpha-olefin * polyene copolymer (A), Preferably it is used in the ratio of 0.5-5 mass parts.

(Crosslinking aid used in combination with sulfur compounds)
When using a sulfur type compound as a crosslinking agent, combined use with a crosslinking accelerator is preferable. Examples of the crosslinking accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazole sulfenamide, N, N′-diisopropyl-2-benzothiazole sulfenamide, 2- Thiazole compounds such as mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyl-disulfide; diphenylguanidine, Guanidine compounds such as triphenyl guanidine and diorthotolyl guanidine; Aldehyde amine compounds such as acetaldehyde-aniline condensate and butyraldehyde-aniline condensate; Imidazoline compounds such as 2-mercaptoimidazoline; Diethyl Thiourea compounds such as urea and dibutylthiourea; thiuram compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; dithioacid salt compounds such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate and tellurium diethyldithiocarbamate; dibutylxanthogen Examples thereof include xanthate compounds such as zinc acid; These crosslinking accelerators are usually used in a proportion of 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass, with respect to 100 parts by mass of the ethylene / α-olefin / polyene copolymer (A). .

(B-3) SiH group-containing compound The SiH group-containing compound (hydrosilyl group-containing compound) is not particularly limited in its molecular structure, and has been conventionally produced, for example, linear, cyclic, branched or three-dimensional Although a resinous material having a network structure can be used, it is necessary that one molecule contains at least 2, preferably 3 or more hydrogen atoms directly bonded to silicon atoms, that is, SiH groups.

  When the crosslinking agent (B) includes (B-3) a SiH group-containing compound, the SiH group-containing compound is usually 0.1 to 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). 100 parts by weight, preferably 0.1 to 75 parts by weight, more preferably 0.1 to 50 parts by weight, still more preferably 0.2 to 30 parts by weight, particularly preferably 0.2 to 20 parts by weight. It is preferred that Adhesive (X) is excellent in a cure rate as it is in the said range. On the other hand, if the SiH group-containing compound is used in a proportion exceeding 100 parts by weight, it may be disadvantageous in terms of cost.

Examples of the SiH group-containing compound according to the present invention include the following general formula (e)
R ⁴ _b H _c SiO _{(4-bc) / 2} (e)
The compound represented by these can be used.

In the general formula (e), R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, excluding an aliphatic unsaturated bond. In addition to the alkyl group exemplified for R ¹ , a phenyl group and a halogen-substituted alkyl group such as a trifluoropropyl group can be exemplified. Of these, a methyl group, an ethyl group, a propyl group, a phenyl group, and a trifluoropropyl group are preferable, and a methyl group and a phenyl group are particularly preferable.

  In the general formula (e), b is 0 ≦ b <3, preferably 0.6 <b <2.2, particularly preferably 1.5 ≦ b ≦ 2, and c is 0 <c ≦ 3, preferably 0.002 ≦ c <2, particularly preferably 0.01 ≦ c ≦ 1, and b + c is 0 <b + c ≦ 3, preferably 1.5 <b + c ≦ 2.7. .

The (B-3) SiH group-containing compound that can be used as a component of the crosslinking agent (B) preferably has 2 to 1000 silicon atoms, particularly preferably 2 to 300 silicon atoms, and most preferably 1 molecule. 2 to 200 organohydrogenpolysiloxanes are preferred, for example 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane, 1,3,5 , 7,8-Pentamethylpentacyclosiloxane and other siloxane oligomers; molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain Silanol group-blocked methyl hydrogen polysiloxane at both ends, Silanol group-blocked dimethylsiloxane at both ends of molecular chain・ Methylhydrogensiloxane copolymer, dimethylhydrogensiloxy group-capped dimethylpolysiloxane with molecular chain at both ends, dimethylhydrogensiloxy group-capped methylhydrogenpolysiloxane with molecular chain at both ends, dimethylhydrogensiloxy group-capped dimethyl with molecular chain at both ends Siloxane / methylhydrogensiloxane copolymer, consisting of R ⁴ ₂ (H) SiO _1/2 units and SiO _4/2 units, optionally R ⁴ ₃ SiO _1/2 units, R ⁴ ₂ SiO _2/2 units , R ⁴ (H) SiO _2/2 units, silicone resins that may contain (H) SiO _3/2 or R ⁴ SiO _3/2 units.

Examples of the trimethylsiloxy group-capped methylhydrogen polysiloxane having both molecular chain terminals include, for example, a compound represented by the following general formula (f), and further, a part or all of the methyl groups in the following general formula (f) are ethyl groups, Examples include compounds substituted with a propyl group, a phenyl group, a trifluoropropyl group, and the like.
(CH ₃ ) ₃ SiO — (— SiH (CH ₃ ) —O—) _d —Si (CH ₃ ) ₃ (f)
[D in the formula (f) is an integer of 2 or more. ]

As the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with trimethylsiloxy groups at both ends of the molecular chain, a compound represented by the following general formula (g), and a part or all of the methyl groups in the following general formula (g) And a compound substituted with a group, a propyl group, a phenyl group, a trifluoropropyl group, and the like.
(CH ₃ ) ₃ SiO — (— Si (CH ₃ ) ₂ —O—) _e — (— SiH (CH ₃ ) —O—) _f —Si (CH ₃ ) ₃ (g)
[In formula (g), e is an integer of 1 or more, and f is an integer of 2 or more. ]

Examples of the molecular hydrogen-terminated silanol group-blocked methylhydrogenpolysiloxane include, for example, a compound represented by the following general formula (h), and further a part or all of the methyl group in the following general formula (h) is an ethyl group, a propyl group, And compounds substituted with a phenyl group, a trifluoropropyl group, and the like.
HOSi (CH ₃ ) ₂ O — (— SiH (CH ₃ ) —O—) ₂ —Si (CH ₃ ) ₂ OH (h)

Examples of the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with silanol groups at both ends of the molecular chain include, for example, a compound represented by the following general formula (i), and further a part or all of the methyl group in the following general formula (i): And compounds substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, and the like.
_{HOSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 2 OH ... (i)
[In formula (i), e is an integer of 1 or more, and f is an integer of 2 or more. ]

Examples of dimethylpolysiloxane blocked with a dimethylhydrogensiloxy group at both ends of the molecular chain include, for example, a compound represented by the following general formula (j), and further a part or all of the methyl group in the following general formula (j) is an ethyl group or propyl And a compound substituted with a group, a phenyl group, a trifluoropropyl group, and the like.
HSi (CH ₃ ) ₂ O — (— Si (CH ₃ ) ₂ —O—) _e —Si (CH ₃ ) ₂ H (j)

Note that e in the formula (j) is an integer of 1 or more.
Examples of the dimethylhydrogensiloxy group-blocked methylhydrogen polysiloxane having both molecular chain terminals include, for example, a compound represented by the following formula (k), and further a part or all of the methyl group in the following formula (k) is an ethyl group or a propyl group. , A phenyl group, a trifluoropropyl group, and the like.
HSi (CH ₃ ) ₂ O — (— SiH (CH ₃ ) —O—) _e —Si (CH ₃ ) ₂ H (k)
[In the formula (k), e is an integer of 1 or more. ]

Examples of the dimethylhydrogensiloxy group-blocked dimethyl siloxane / methyl hydrogen siloxane copolymer having both ends of the molecular chain include, for example, a compound represented by the following general formula (l), and a part of the methyl group in the following general formula (l): Examples thereof include compounds in which all are substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, or the like.
HSi (CH ₃ ) ₂ O — (— Si (CH ₃ ) ₂ —O—) _e — (— SiH (CH ₃ ) —O—) _h —Si (CH ₃ ) ₂ H (l)
[In the formula (l), e and h are each an integer of 1 or more. ]

  Such a SiH group-containing compound can be produced by a known method, for example, octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane and hexamethyldisiloxane or 1,3-dihydrohydride which can be a terminal group. -1,1,3,3-tetramethyldisiloxane and other compounds containing a triorganosilyl group or diorganohydrogensiloxy group in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid It can be easily obtained by equilibrating at a temperature of about −10 ° C. to + 40 ° C.

Such SiH group-containing compounds can be used alone or in combination of two or more.
When the crosslinking agent (B) contains a SiH group-containing compound, it preferably contains a catalyst used for the hydrosilylation reaction together with the SiH group-containing compound, and preferably contains a reaction inhibitor that controls the reaction.

(Hydrosilylation catalyst used in combination with SiH group-containing compound)
When the crosslinking agent (B) contains (B-3) a SiH group-containing compound, it is also preferred to contain a catalyst (hydrosilylation catalyst) used in the hydrosilylation reaction.

  The hydrosilylation catalyst is an addition reaction catalyst that promotes the addition reaction (alkene hydrosilylation reaction) between the alkenyl group in the ethylene / α-olefin / polyene copolymer (A) and the SiH group of the SiH group-containing compound. If it does, there is no restriction | limiting in particular, For example, the addition reaction catalyst which consists of platinum group elements, such as a platinum-type catalyst, a palladium-type catalyst, a rhodium-type catalyst (periodic table group 8 metal, a group 8 metal complex, a group 8 metal compound Group 8 metal-based catalysts). In the present invention, it is desirable to use a complex of a group 8 element metal of the periodic table and a compound containing a vinyl group and / or a carbonyl group. As the group 8 element metal of the periodic table, platinum is particularly preferable.

  The platinum-based catalyst may be a known one that is usually used for addition-curing type curing, such as a finely powdered platinum metal catalyst described in US Pat. No. 2,970,150, US Pat. No. 2,823, No. 218, chloroplatinic acid catalyst, U.S. Pat. No. 3,159,601 and U.S. Pat. No. 159,662, complex compounds of platinum and hydrocarbons, U.S. Pat. Complex of chloroplatinic acid and olefin described in US Pat. No. 5,516,946, platinum and vinylsiloxane described in US Pat. No. 3,775,452 and US Pat. No. 3,814,780 And complex compounds. More specifically, examples include platinum alone (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, or a carrier such as alumina or silica on which a platinum carrier is supported.

  As the compound containing a vinyl group, a vinyl group-containing organosiloxane is preferable. Specific examples of complexes of these with platinum include platinum-divinyltetramethyldisiloxane complex, platinum-divinyltetraethyldisiloxane complex, platinum-divinyltetrapropyldisiloxane complex, platinum-divinyltetrabutyldisiloxane complex, platinum -Divinyltetraphenyldisiloxane complex.

  As the compound containing a carbonyl group, carbonyl, octanal and the like are preferable. Specific examples of the complex of these with platinum include a platinum-carbonyl complex, a platinum-octanal complex, a platinum-carbonylbutyl cyclic siloxane complex, and a platinum-carbonylphenyl cyclic siloxane complex.

  Among the vinyl group-containing organosiloxanes, vinyl group-containing cyclic organosiloxanes are preferable. Examples of the complex of platinum with platinum include a platinum-vinylmethyl cyclic siloxane complex, a platinum-vinylethyl cyclic siloxane complex, and a platinum-vinylpropyl cyclic siloxane complex. The vinyl group-containing organosiloxane itself may be a ligand for a metal, but may be used as a solvent for coordinating other ligands. A complex in which a vinyl group-containing organosiloxane is used as a solvent and the above-mentioned compound containing a carbonyl group is a ligand is particularly preferable as a hydrosilylation catalyst.

  Specific examples of such complexes include a platinum-carbonyl complex vinylmethyl cyclic siloxane solution, a platinum-carbonyl complex vinylethyl cyclic siloxane solution, a platinum-carbonyl complex vinylpropyl cyclic siloxane solution, and a platinum-carbonyl complex divinyl. Tetramethyldisiloxane solution, platinum-carbonyl complex divinyltetraethyldisiloxane solution, platinum-carbonyl complex divinyltetrapropyldisiloxane solution, platinum-carbonyl complex divinyltetrabutyldisiloxane solution, platinum-carbonyl complex divinyltetraphenyldi A siloxane solution is mentioned.

  The hydrosilylation catalyst comprising these complexes may further contain components other than the compound containing a vinyl group and / or a carbonyl group. For example, a solvent other than a compound containing a vinyl group and / or a carbonyl group may be contained. Examples of these solvents include various alcohols and xylene, but are not limited thereto.

  Specific examples of the alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol. , Aliphatic saturated alcohols such as capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and eicosyl alcohol; fats such as allyl alcohol and crotyl alcohol Unsaturated alcohols; cycloaliphatic alcohols such as cyclopentanol and cyclohexanol; benzyl alcohol, cinnamyl alcohol Aromatic alcohols such as Lumpur; and heterocyclic alcohols such as furfuryl alcohol.

  An example of using alcohol as a solvent is a platinum-octanal / octanol complex. By including these solvents, there are advantages such as easy handling of the catalyst and easy mixing with the rubber composition. Among the various hydrosilylation catalysts mentioned above, a vinylmethyl cyclic siloxane solution of a platinum-carbonyl complex (in particular, a complex represented by the following chemical formula 1 is preferable), a platinum-vinylmethyl cyclic siloxane complex (in particular, represented by the following chemical formula 2). A platinum-divinyltetramethyldisiloxane complex (especially a complex represented by the following chemical formula 3), a platinum-octanal / octanol complex and the like are practically preferred, and among them, a platinum-carbonylvinylmethyl cyclic siloxane complex Is particularly preferred.

Chemical formula 1: Pt ⁰ · CO · (CH ₂ ═CH (Me) SiO) ₄
Chemical formula 2: Pt ⁰ · (CH ₂ ═CH (Me) SiO) ₄
Chemical formula 3: Pt ⁰ -1.5 [(CH ₂ ═CH (Me) ₂ Si) ₂ O]
The palladium-based catalyst is composed of palladium, a palladium compound, chloropalladic acid, and the rhodium-based catalyst is composed of rhodium, a rhodium compound, rhodium chloride, and the like.

Examples of hydrosilylation catalysts other than the above include Lewis acids and cobalt carbonyl.
These catalysts can be used alone or in combination of two or more.
The proportion of Group 8 element metal (preferably platinum) contained in these catalysts is usually 0.1 to 10% by weight, preferably 1 to 5% by weight, and more preferably 2 to 4% by weight.
When the crosslinking agent (B-3) contains a hydrosilylation catalyst, the catalyst is usually 0.01 to 10 parts by weight, preferably 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A), preferably It is used in a proportion of 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight. If it is used at a ratio exceeding 10 parts by weight, it is not preferable because it is disadvantageous in cost.

When the catalyst used for the hydrosilylation reaction is used within the above range, an adhesive (X) having excellent processability and curing speed can be formed.
As the crosslinking agent (B) which is a component of the adhesive (X) according to the present invention, the above (B-1), (B-2) and (B-3) may be used alone or in combination of two or more. May be used. In addition to (B-1), (B-2) and (B-3), the crosslinking agent (B) can be used to crosslink the ethylene / α-olefin / polyene copolymer (A). A crosslinking agent may be included. Examples of the crosslinking agent other than (B-1), (B-2) and (B-3) include quinoid crosslinking agents and resin crosslinking agents which are usually used for EPR and EPDM. The crosslinking agent (B) may contain a crosslinking aid other than those described above. When the adhesive (X) contains such a crosslinking agent (B), the adhesion between adherends, at least one of which is a rubber molded body, is particularly good.

  In the present invention, the crosslinking agent (B) is the crosslinking agent (B-1) or (B-3) among the crosslinking agents (B-1), (B-2) and (B-3). The crosslinking agent (B-1) is particularly preferable. When (B-1) which is an organic peroxide and an allyl compound-based crosslinking aid is used as the crosslinking agent (B) constituting the adhesive (X), various rubber molded bodies which are adherends Adhesive (X) having a good adhesion strength and a high adhesion rate can be obtained, whereby a rubber bonded body in which the adherend (1) and the adherend (2) are firmly bonded is obtained. It can be manufactured particularly easily. Moreover, as a crosslinking agent (B-1), it represents with the organic peroxide represented by the said general formula (a) and / or the said general formula (b), and the said formula (c) and / or (d). It is particularly preferable to contain a crosslinking aid.

Additives In addition to the above-mentioned ethylene / α-olefin / polyene copolymer (A) and crosslinking agent (B), the adhesive (X) according to the present invention contains various additives according to the desired properties. You may add suitably.

  Examples of the additive include various additives that can be added to EPDM and the like. Examples include antifoaming agents, reaction inhibitors, silane coupling agents, plasticizers, stabilizers, tackifiers, reinforcing agents, fillers, and the like.

(Defoamer)
As the antifoaming agent that can be added to the adhesive (X) according to the present invention, those used for non-aqueous systems can be used, and representative examples include silicones such as dimethylpolysiloxane, modified butadienes, Examples thereof include ether-based, acrylic-based, vinyl-based, and mixed systems thereof. These can be obtained from Shin-Etsu Silicone, Toray Dow Corning, Kao, Sanyo Kasei, Enomoto Kasei, Nisshin Chemical Research Laboratories, etc.

  When the adhesive (X) according to the present invention includes an antifoaming agent, the adhesive (X) is prepared, and when the adhesive (X) is applied to the adherend surface, and each of bonding and crosslinking In the process, foaming due to air entering between the adherends can be suppressed, and improvement in work efficiency is expected.

  When the adhesive (X) contains an antifoaming agent, 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). More preferably, it can be in the range of 0.2 to 1.0 part by weight.

(Reaction inhibitor)
The adhesive (X) according to the present invention may contain a known reaction inhibitor as an optional component as long as the object of the present invention is not impaired. The adhesive (X) according to the present invention can be used in such a manner that the adherends are usually bonded to each other after being applied to the surface of the adherend and crosslinked, and if necessary, the reaction can be achieved by including a reaction inhibitor. Can be appropriately controlled.

  The reaction inhibitor is not particularly limited. For example, benzotriazole, ethynyl group-containing alcohol (for example, 1-ethynyl-2-ethyl-1-hexanol, ethynylcyclohexanol), acrylonitrile, amide compound (for example, N, N -Dialylacetamide, N, N-diallylbenzamide, N, N, N ', N'-tetraallyl-o-phthalic acid diamide, N, N, N', N'-tetraallyl-m-phthalic acid diamide, N, N , N ', N'-tetraallyl-p-phthalic acid diamide, etc.), sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, tetramethyltetravinylcyclotetrasiloxane, hydroperoxide, etc. An organic peroxide etc. are mentioned.

These reaction inhibitors can be used alone or in combination of two or more.
Although it does not specifically limit when adhesive agent (X) contains a reaction inhibitor, Usually 0-50 weight part with respect to 100 weight part of ethylene * alpha-olefin * polyene copolymer (A), Preferably it is 0.00. 0001-50 parts by weight, more preferably 0.0001-30 parts by weight, still more preferably 0.0001-20 parts by weight, particularly preferably 0.0001-10 parts by weight, most preferably 0.0001-5 parts by weight. Used in proportions. When used in a proportion of 50 parts by weight or less, the crosslinking rate is moderate and adhesion of the adherend using the adhesive (X) is suitably performed. If it exceeds 50 parts by weight, it may be disadvantageous in terms of cost.

(Silane coupling agent)
The adhesive (X) according to the present invention can contain a known silane coupling agent as an optional component as long as the object of the present invention is not impaired. A silane coupling agent is usually used for the purpose of further improving self-adhesion. Examples of the silane coupling agent include an acrylic (methacrylic) functional silane coupling agent, an epoxy functional silane coupling agent, and an amino (imino) functional silane coupling agent.

  Specific examples of acrylic (methacrylic) functional silane coupling agents include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxy. Examples include silane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.

  Specific examples of the epoxy functional silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

Specific examples of amino (imino) functional silane coupling agents include H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si An amino group such as (OC ₂ H ₅ ) ₃ and / or an imino group-containing alkoxysilane; the amino group and / or imino group-containing alkoxysilane;

のようなエポキシシラン化合物との反応生成物；前記アミノ基および（または）イミノ基
含有アルコキシシランと、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₃)₃ 、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯＣＨ₂ＣＨ₂ＣＨ₂Ｓｉ（ＯＣＨ₂ＣＨ₂ＯＣＨ₃)₃のようなメタクリルオキシシラン化合物との反応生成物などが挙げられる。

A reaction product with an epoxy silane compound such as: an aminosilane and / or imino group-containing alkoxysilane, and CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CH ₂ ═ Examples thereof include a reaction product with a methacryloxysilane compound such as C (CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ .

  When the adhesive (X) contains a silane coupling agent, it is not particularly limited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A), More preferably, it is used in a proportion of 0.1 to 5 parts by weight.

(Plasticizer)
The adhesive (X) according to the present invention can contain a known plasticizer as an optional component as long as the object of the present invention is not impaired.

  Specifically, for example, paraffinic process oil, naphthenic process oil, aromatic process oil, α-olefin, α-olefin oligomer, α-olefin having a functional group at its terminal or oligomer thereof, ethylene and α- Petroleum softeners such as olefin co-oligomers, paraffin wax, liquid paraffin, white oil, petrolatum, lubricating oil, petroleum asphalt, and petroleum jelly; coal tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, Fat oil-based softeners such as rapeseed oil and coconut oil; tall oil; synthetic polymer materials such as petroleum resin, atactic polypropylene and coumarone indene resin; phthalic acid derivatives, isophthalic acid derivatives, tetrahydrophthalic acid derivatives, adipic acid derivatives , Azelaic acid derivatives, sebacin Derivatives, dodecane-2-acid derivatives, maleic acid derivatives, fumaric acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, citric acid derivatives, itaconic acid derivatives, oleic acid derivatives, ricinoleic acid derivatives, stearic acid derivatives, phosphoric acid derivatives , Sulfonic acid derivatives, glycerin derivatives, glutaric acid derivatives, epoxy derivatives, glycol derivatives, paraffin derivatives, silicone oils, and the like.

  Among them, α-olefins, α-olefin oligomers, α-olefins having functional groups at their terminals or oligomers thereof, ethylene and α-olefin co-oligomers, process oils, paraffin derivatives, which do not inhibit the silylation reaction. In particular, paraffinic process oils, α-olefins, α-olefin oligomers, α-olefins having functional groups at their terminals or oligomers thereof, and co-oligomers of ethylene and α-olefins are preferably used. In particular, a plasticizer that does not inhibit the hydrosilylation reaction is preferable. Specifically, a plasticizer in which the content of a sulfur compound, a nitrogen compound, an amine compound, and a phosphorus compound is 100 ppm or less is preferable.

  When the adhesive (X) according to the present invention contains a plasticizer, it is not particularly limited, but usually 0 to 1000 parts by weight, preferably 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). Is used in a proportion of 1 to 1000 parts by weight, more preferably 5 to 800 parts by weight, still more preferably 10 to 700 parts by weight, particularly preferably 20 to 500 parts by weight, and most preferably 30 to 300 parts by weight. When used in the above ratio, the fluidity is improved and the coating property is improved.

(Stabilizer)
The adhesive (X) according to the present invention can contain various known stabilizers as optional components as long as the object of the present invention is not impaired.

  Examples of the stabilizer used as necessary include a heat resistance stabilizer, a weather resistance stabilizer, a hindered amine stabilizer, and the like. Examples of the heat-resistant stabilizer used as necessary in the present invention include a phenol-based stabilizer, a phosphorus-based stabilizer, and a sulfur-based stabilizer.

  As the phenol-based stabilizer, a phenol-based stabilizer conventionally used as a stabilizer is used without any particular limitation. Specific examples of the phenol-based stabilizer include β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester, tetrakis [methylene-3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-t-hydroxybenzyl) benzene, dl-α-tocopherol, tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, tris [(3,5-di -T-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl) -4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-spiro [5.5] undecane is preferred.

  Commercially available products may be used as the phenol-based stabilizer, such as Irganox 1010 (Irganox 1010, Ciba Geigy, Trademark), Irganox 1035 (Irganox 1035, Ciba Geigy, Trademark), Irganox 1076 (Irganox 1076, Ciba Geigy, Trademark), Irganox, and the like. 1135 (Irganox 1135, Ciba-Geigy, Trademark), Irganox 1330 (Irganox 1330, Ciba-Geigy, Trademark), Irganox 3114 (Irganox 3114, Ciba-Geigy, Trademark), Irganox 3125 (Irganox 3125, Ciba-Geigy H, Trademark, B) ), Trademark), Cyanox 1790 (Cyanox 1790, Cyanamid Co., Ltd.), Smizer A-80 (SumilizerGA-80, Sumitomo Chemical Co., trademark), vitamin E (Eisai Co.) and the like. These phenolic stabilizers can be used alone or in combination.

  The blending amount of the phenol-based stabilizer is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). Is preferably 0.1 to 3 parts by weight. When the content of the phenol-based stabilizer is in the above range with respect to 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A), stability such as heat resistance and aging resistance is improved. It is highly effective and the cost of the stabilizer can be kept low.

  As the phosphorus stabilizer, phosphorus stabilizers conventionally used as stabilizers are used without any particular limitation. Commercially available products may be used as the phosphorus-based stabilizer, such as Irgafos 168 (Irgafos 168, Ciba Geigy, Trademark), Irgafos 12 (Irgafos 12, Ciba Geigy, Trademark), Irgafos 38 (Irgafos 38, Ciba Geigy, Trademark), Mark 329K (Mark 329K, Asahi Denka Co., Ltd., trademark), Mark PEP36 (Mark PEP36, Asahi Denka Co., Ltd., trademark), Mark PEP-8 (Mark PEP-8, Asahi Denka Co., Ltd., trademark), Sandstab P- EPQ (Clariant, trademark), Weston 618 (Weston 618, GE, trademark), Weston 619G (Weston 619G, GE, trademark), Weston-624 (Weston-624, GE, trademark), and the like. These phosphorus stabilizers can be used alone or in combination.

  The compounding amount of the phosphorus stabilizer is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). Is preferably 0.1 to 3 parts by weight. When the content of the phosphorus stabilizer is within the above range with respect to 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A), stability such as heat resistance and aging resistance is improved. The improvement effect is high, the cost of the stabilizer is kept low, and the properties of the ethylene / α-olefin / polyene copolymer (A), such as heat resistance, are not lowered.

  As the sulfur stabilizer, a sulfur stabilizer conventionally used as a stabilizer is used without any particular limitation. Specific examples of the sulfur stabilizer include dialkylthiodipropionates such as dilauryl-, dimyristyl-, and distearyl- and polyhydric alcohols of alkylthiopropionic acids such as butyl-, octyl-, lauryl-, and stearyl- Examples thereof include esters of glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralauryl thiopropionate).

  Commercially available products may be used as the sulfur stabilizer, such as DSTP (Yoshitomi) (Yoshitomi Pharmaceutical Co., Ltd., Trademark), DLTP (Yoshitomi) (Yoshitomi Pharmaceutical Co., Ltd., Trademark), DLTOIB (Yoshitomi Pharmaceutical). (Co., Ltd., Trademark), DMTP (Yoshitomi) (Yoshitomi Pharmaceutical Co., Ltd., Trademark), Seenox 412S (Shiraishi Calcium Co., Ltd., Trademark), Cyanox 1212 (Cyanamide, Trademark) and the like. These sulfur stabilizers can be used alone or in combination.

  The amount of the sulfur stabilizer is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). Is preferably 0.1 to 3 parts by weight. When the content of the sulfur stabilizer is within the above range with respect to 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A), stability such as heat resistance and aging resistance is improved. The effect is high, the cost of the stabilizer is kept low, and the properties of the ethylene / α-olefin / polyene copolymer (A), such as heat resistance, are not lowered.

The weathering stabilizer used as necessary in the present invention is roughly classified into an ultraviolet absorber and a light stabilizer.
Specific examples of the UV absorber include salicylic acid UV absorbers, benzophenone UV absorbers, benzotriazole absorbers, and cyanoacrylate UV absorbers.

  The ultraviolet absorber is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). Used in a proportion of ~ 3 parts by weight. A conventionally known light stabilizer can be used as the light stabilizer, and among them, a hindered amine light stabilizer (HALS) is preferably used. Specific examples of the hindered amine light stabilizer include the following compounds.

  Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate , Poly {[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2-4-diyl] [(2,2,6,6-tetramethyl-4- Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 , 4-butanetetracarboxylate, 1,1 ′-(1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), mixed {2,2,6,6-tetramethyl -4-piperidyl / β, β, β ′, β '-Tetramethyl-3-9- [2,4,8,10-tetraoxaspiro (5.5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, poly {[6-N -Morpholyl-1,3,5-triazine-2-4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl -4-piperidyl) imino]} and a condensate of N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane.

These hindered amine light stabilizers are used alone or in combination.
The amount of the hindered amine light stabilizer is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A). The amount is preferably 0.1 to 3 parts by weight. When the content of the hindered amine light stabilizer is within the above range with respect to 100 parts by weight of the ethylene / α-olefin / polyene copolymer (A), stability such as heat resistance and aging resistance is improved. The improvement effect is high, and the cost of the light stabilizer can be kept low.

(Reinforcing agent)
The adhesive (X) according to the present invention may contain a known reinforcing agent as an optional component as long as the object of the present invention is not impaired.

  As the reinforcing agent, a known rubber reinforcing agent used for the purpose of enhancing mechanical properties such as tensile strength, tear strength, and abrasion resistance can be appropriately used. Specifically, for example, SRF, GPF, FEF, Examples thereof include carbon blacks such as HAF, ISAF, SAF, FT, and MT, carbon blacks that have been surface-treated with a silane coupling agent, finely divided silicic acid, silica, and the like.

(filler)
The adhesive (X) according to the present invention may contain a known filler as an optional component as long as the object of the present invention is not impaired.

  As the filler, both inorganic fillers and organic fillers can be used, and specific examples include organic fillers, inorganic fillers, light calcium carbonate, heavy calcium carbonate, talc, clay and the like.

Other compounding components The adhesive (X) according to the present invention is within the range not impairing the object of the present invention, and the above-mentioned ethylene / α-olefin / polyene copolymer (A), cross-linking agent (B), and as necessary. In addition to the additive added, other compounding components such as a resin component other than the copolymer (A) and a solvent may be contained.

  The resin component other than the copolymer (A) is not particularly limited, and examples thereof include an ethylene / α-olefin / polyene copolymer having a viscosity at 25 ° C. of 5,000 Pa · s or more. It is done.

  As the solvent, a solvent having excellent compatibility or dispersibility with each component constituting the adhesive can be appropriately used. However, in the adhesive according to the present invention, the content of the solvent is preferably small and substantially It is more preferable not to contain a solvent.

  The adhesive (X) according to the present invention is mainly composed of an ethylene / α-olefin / polyene copolymer (A) having a viscosity at 25 ° C. of 1 Pa · s or more and less than 5,000 Pa · s. It is included and is substantially liquid. Such an adhesive (X) preferably does not substantially contain a solvent such as an organic solvent.

  The adhesive (X) according to the present invention is produced by adjusting the viscosity and amount ratio of the blending components so as to have an appropriate application performance according to the shape and material of the adherend to which the adhesive (X) is applied. can do.

  The viscosity at 25 ° C. of the adhesive (X) is not particularly limited, but is usually in the range of 0.1 Pa · S or more and less than 2000 Pa · S, preferably 0.2 Pa · S or more and 1000 Pa · s. The range is less than S.

  The adhesive (X) according to the present invention is suitably used for the production of a rubber bonded body, and has good adhesion even when the adherend is a sulfur vulcanized rubber molded body, which has conventionally been difficult to firmly bond. Showing gender. The adhesive (X) according to the present invention can provide a high degree of adhesiveness by applying and bonding to at least one adhesive surface of an adherend to be bonded and then crosslinking by heating.

<Adherent (1)>
The adherend (1) constituting the rubber bonded body of the present invention is a rubber molded body.
The rubber component constituting the adherend (1) includes natural rubber (NR), isoprene rubber such as isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber ( NBR), conjugated diene rubbers such as chloroprene rubber (CR); ethylene / α-olefin rubbers such as ethylene / propylene random copolymer rubber (EPR) and ethylene / α-olefin / polyene copolymers (for example, EPDM) Copolymer rubbers can be mentioned, and these may be included singly or in combination of two or more.

  These rubber components may be crosslinked or non-crosslinked, but are preferably crosslinked, and particularly preferably crosslinked using sulfur or a sulfur-based compound.

  For the adherend (1), in addition to the rubber component, conventionally known compounding agents such as reinforcing agents, fillers, softeners, crosslinking agents, crosslinking accelerators, crosslinking aids, processing aids, pigments, aging Additives usually used in the production of rubber, such as an inhibitor, may be appropriately blended as long as the object of the present invention is not impaired.

  When the rubber component contained in the adherend (1) is crosslinked using a crosslinking agent or contains a crosslinking agent, examples of the crosslinking agent include known crosslinking agents such as sulfur compounds and organic peroxides. Specifically, examples of the crosslinking agent (B) included in the above-described adhesive (X) can include the crosslinking agents exemplified. Of these, sulfur-based crosslinking agents such as sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, and selenium dithiocarbamate are preferred as the crosslinking agent. Moreover, the rubber | gum component contained in a to-be-adhered body (1) may use the crosslinking adjuvant illustrated as what can be added to a crosslinking agent (B).

  In the rubber bonded body according to the present invention, when the adherend (1), which is a rubber molded body, is a crosslinked rubber molded body, it may be a previously crosslinked molded body, or when bonding with an adhesive is performed. It may be crosslinked with an adhesive. Among the crosslinked rubber molded bodies, a rubber molded body crosslinked with a sulfur-based crosslinking agent such as sulfur is particularly preferable.

The adherend (1) is not particularly limited, and any one molded by a known method for molding a rubber composition can be used.
The shape of the adherend (1) may be any shape, and the adhesion surface with the adherend (2) may be flat or may have a complicated shape. It is preferable that the adherend (1) has a sheet shape because the adhesive (X) can be easily applied and the adhesive (X) can be easily and uniformly crosslinked after application.

<Adherend (2)>
The adherend (2) constituting the rubber bonded body according to the present invention may be a rubber molded body or a molded body formed of a material other than rubber. Examples of the rubber molded body include those similar to the adherend (1). When the adherend (2) is a molded body formed of a material other than rubber, the material is not particularly limited as long as it can form an adhesive body with the adherend (1) which is a rubber molded body. Anything is acceptable.

  The material of the adherend (2) may be any material such as rubber, thermoplastic resin, thermosetting resin, metal, ceramic, glass, wood, paper, cloth, and composites thereof. A rubber, a thermoplastic resin, a thermosetting resin or a composite containing these is preferable, more preferably a rubber, still more preferably a crosslinked rubber, and particularly preferably a sulfur-crosslinked rubber.

  The rubber bonded body according to the present invention is not limited as long as the bonded body (1) and the bonded body (2) are bonded to form an bonded body, and the bonded body (1) and the bonded body (2). ) May have any shape. In the present invention, since the above-mentioned adhesive (X) excellent in applicability is used as an adhesive for adhering the adherend (1) and the adherend (2), the adhesive surface has a complicated shape. However, an adhesive body can be manufactured easily.

  The shapes of the adherend (1) and the adherend (2) may be any shape as long as they can be bonded together, and are not particularly limited. Also, the shape of the bonding surface is not particularly limited as long as it is a shape that can be bonded, and a desired shape such as a planar shape, a curved surface shape, a porous body, a woven fabric shape, and an uneven shape can be adopted. it can.

  In the present invention, it is preferable that either one of the adherend (1) and the adherend (2) constituting the rubber bonded body, preferably both are sheet-like. When at least one of the adherend (1) and the adherend (2) is in the form of a sheet, it is easy to bond them together, and in the step of crosslinking the adhesive, heat is uniformly transmitted and uniform. Crosslinking is easy and can be performed in a short time, and is excellent in adhesion. In the case where the rubber bonded body is formed from the adherend (1) and the adherend (2) which are sheet-like cross-linked rubber molded bodies, the adhesiveness is particularly excellent, which is preferable.

<Manufacture of rubber adhesives>
In the rubber bonded body manufacturing method of the present invention, the above-mentioned adherend (1) and adherend (2) are bonded using the above-described adhesive (X) to manufacture a rubber bonded body.

  In the method for producing a rubber bonded body, the step of applying the adhesive (X) to the bonding surface of the adherend, the step of bonding the adherends together via the adhesive (X), and the adhesive (X) A step of crosslinking.

Application Step The application step is the above-described adhesive (X), that is, an ethylene / α-olefin / polyene copolymer (A) having a viscosity at 25 ° C. of 1 Pa · s or more and less than 5,000 Pa · s. And an adhesive (X) containing a crosslinking agent (B) is applied to one or both of the adhesion surfaces of the adherend (1) and the adherend (2).

It is preferable that the adhesive (X) is prepared so that it can be easily applied according to the shape and material of the adhesion surface of the adherend to be applied.
The method for applying the adhesive (X) is not particularly limited, and it can be applied by a known method using a brush, roll, spatula, sponge, spray, bar coater or the like.
The amount of application is not particularly limited, and an amount capable of obtaining good adhesiveness can be appropriately selected.

Bonding step The bonding step is to bond the adherend (1) and the adherend (2) that have undergone the coating step of applying the adhesive (X) to at least one bonding surface via the adhesive (X). This can be done by bringing the surfaces into close contact. In the bonding step, the adhesive surfaces may simply be brought into contact with each other via the adhesive (X), but it is preferable to apply pressure.

In the crosslinking step , the adhesive (X) is crosslinked in a state where the adherend (1) and the adherend (2) are bonded together via the adhesive (X). Cross-linking of the adhesive (X) is easy by applying sufficient heat for cross-linking to the adhesive (X) part, although it depends on the type and amount of the cross-linking agent (B) contained in the adhesive (X). Can be done. The crosslinking of the adhesive (X) may be performed by heating the entire rubber bonded body, or may be performed by heating under a condition in which only the adhesive application portion and its periphery are heated.

  The crosslinking step is not particularly limited, but is preferably performed under pressure because it is easy to obtain strong adhesiveness. The pressurizing condition is not particularly limited, but it is usually 0.01 to 5 MPa, preferably 1 to 3 MPa. The pressurization in the cross-linking step may be performed by a method in which pressure is applied to the bonding surface via the adhesive (X), and for example, a method such as press or roll press can be preferably employed.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the present invention, each physical property was measured or evaluated as follows.

・ Viscosity (Pa · s)
In accordance with JIS K7117-2, using an E-type viscometer (TVW-25) manufactured by Toki Sangyo Co., Ltd., cone plate (angle: 1 degree × R24 mm or 3 degrees × R14 mm), rotation speed: 0 0.1 to 100 rpm, sample amount: measured at 25 ° C. under the conditions of 0.6 to 1.0 g, and the value showing the same value for 30 seconds or more was taken as the viscosity.

・ Workability (applicability)
The adhesive had sufficient fluidity, and it was evaluated as good (◯) if it could be applied to the coated surface of the adherend without any difficulty using a spatula, and poor (×) if it could not be applied.

・ Environmental hygiene When a rubber laminate, which is an adhesive, is placed on a hot plate at 80 ° C. and held for 5 minutes, the solvent smells bad (×). What did not have a solvent odor was evaluated as good (◯).

-Adhesiveness The adhesive strength of the rubber laminate as an adhesive was evaluated. The evaluation method was evaluated by cutting an adhesive interface portion of an EPDM molded sheet, which is an adhesive body, with a cutter, and peeling the EPDM molded sheet on one side with a 180-degree peel as a trigger. Good (○) when the resin part cohesively breaks when peeling. Those that peeled straight without cohesive failure were evaluated as bad (x), and those that peeled off but were resistant were evaluated as slightly defective (Δ).

[Example 1]
<Production of ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1)>
Using a stainless steel polymerization vessel (stirring rotation speed = 250 rpm) having a substantial internal volume of 100 liters equipped with stirring blades, ethylene, propylene and 5-vinyl-2-norbornene (hereinafter abbreviated as VNB) Original copolymerization was performed. From the side of the polymerization vessel to the liquid phase, 42 liters of hexane per hour, 2.1 kg of ethylene, 1.9 kg of propylene, 400 g of VNB, 515 liters of hydrogen, 280 mmol of VOCl ₃ as a catalyst, Al (Et) ₂ Cl was continuously fed at a rate of 840 mmol and Al (Et) _1.5 Cl _1.5 at a rate of 840 mmol. The polymerization temperature was 45 ° C., and the polymerization pressure was 7.5 kgf / cm ² (0.75 MPa).

When the copolymerization reaction was performed under the conditions described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1) was obtained in a uniform solution state.
Thereafter, a small amount of methanol is added to the polymerization solution continuously extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the polymer is separated from the solvent by a steam stripping treatment, followed by vacuum drying at 55 ° C. for 48 hours. Went.

  The ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1) thus obtained had an ethylene unit [i] / α-olefin unit [ii] molar ratio ([i] / [ii]). Is 61.5 mol% / 37.0 mol%, iodine value is 10.0 g / 100 g, intrinsic viscosity [η] (in 135 ° C. decalin solution) is 0.27 (dl / g), Mn: 3160, viscosity is 830 Pa · s.

<Preparation of adhesive>
100 parts by weight of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1) obtained above and 2,5-dimethyl-2,5-di ( t-Butylperoxy) hexane (trade name: Kayahexa AD, manufactured by Kayaku Akzo Co., Ltd.) and 1 part by weight of a crosslinking assistant, triallyl isocyanurate (TAIC (registered trademark), manufactured by Nippon Kasei Co., Ltd.) Were mixed with stirring at 2000 rpm for 10 minutes at room temperature at a room temperature using a stirrer (Awatori Nertaro (registered trademark) ARE-250, manufactured by THINKY), and then defoamed at 2200 rpm for 1 minute. Thus, a liquid EPDM adhesive A was obtained.

<Manufacture of adhesives>
As an adherend, two EPDM molded sheets (50 mm × 50 mm, thickness 2 mm) formed by carbon-containing sulfur vulcanization were prepared. Of these, 1 g of the liquid EPDM adhesive A was dropped on one side of one EPDM molded sheet, and stretched and applied uniformly over the entire sheet surface using a spatula. Thus, another EPDM molded sheet (without adhesive application) was bonded to the EPDM molded sheet coated with the adhesive A through the coated adhesive A and laminated. This was crosslinked under the conditions of a pressure of 1 MPa, a temperature of 170 ° C., and a time of 30 minutes to obtain an adhesive body as a laminate.
The evaluation results are shown in Table 1.

[Example 2]
<Production of ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-2)>
Using a stainless steel polymerization vessel (stirring rotation speed = 250 rpm) with a substantial internal volume of 100 liters equipped with stirring blades, three of ethylene, propylene and 5-vinyl-2-norbornene (hereinafter abbreviated as VNB) are continuously used. Original copolymerization was performed. From the side of the polymerization vessel to the liquid phase, 60 liters of hexane per hour, 1.3 kg of ethylene, 2.5 kg of propylene, 130 g of VNB, 30 liters of hydrogen, 23 VO (OEt) Cl ₂ as a catalyst Mmol, Al (Et) _1.5 Cl _1.5 was fed continuously at a rate of 161 mmol. The copolymerization reaction was carried out under the conditions described above and in Table 1 to obtain an ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-2) in a homogeneous solution state. Thereafter, a small amount of methanol is added to the polymerization solution continuously withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction, and the polymer is separated from the solvent by a steam stripping treatment, followed by vacuum drying at 55 ° C. for 48 hours. Was done.

  The ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A2) thus obtained had an ethylene unit [i] / α-olefin unit [ii] molar ratio ([i] / [ii]) of 63. 0.5 mol% / 33.0 mol%, iodine value was 23.5 g / 100 g, intrinsic viscosity (in 135 ° C. decalin solution) was 0.08 dl / g, Mn was 920, and viscosity was 10 Pa · s.

<Preparation of adhesive>
In the preparation of the adhesive of Example 1, the ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-2) obtained above was used instead of the copolymer (A-1). Otherwise, a liquid EPDM adhesive B was obtained.

<Manufacture of adhesives>
In the production of the adhesive body of Example 1, an adhesive body as a laminate was obtained in the same manner except that the liquid EPDM adhesive B obtained above was used instead of the adhesive A.
The evaluation results are shown in Table 1.
[Example 3]

<Preparation of adhesive>
100 parts by weight of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1) obtained in Example 1, sulfur (1.5 parts by weight) as a crosslinking agent, and 2-mercapto as a crosslinking aid 0.5 parts by weight of benzothiazole (trade name: Sunseller M, manufactured by Sanshin Chemical Industry Co., Ltd.), 1.0 part by weight of tetramethylthiuram disulfide (trade name: Sunseller TT, manufactured by Sanshin Chemical Industry Co., Ltd.) Mixing 5.0 parts by weight of zinc oxide, stirring and mixing at 2000 rpm for 10 minutes at room temperature, using a stirrer (THINKY Co., Ltd., Awatori Netaro (registered trademark) ARE-250), Subsequently, defoaming was performed at 2200 rpm for 1 minute to obtain a liquid EPDM adhesive C.

<Manufacture of adhesives>
In the production of the adhesive body of Example 1, an adhesive body as a laminate was obtained in the same manner except that the liquid EPDM adhesive C obtained above was used instead of the adhesive A.
The evaluation results are shown in Table 1.
[Example 4]

<Preparation of adhesive>
100 parts by weight of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-2) obtained in Example 2 and a SiH group-containing crosslinking agent (compound of the following formula p, trade name: X93-916, 4.3 parts by weight of Shin-Etsu Chemical Co., Ltd.), reaction inhibitor (compound of formula q below, trade name: X93-1036, manufactured by Shin-Etsu Chemical Co., Ltd.) and hydrosilylation reaction catalyst (1, 3, 5 , 7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane-platinum complex (2% platinum catalyst), trade name: X93-1410, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.4 parts by weight The mixture was mixed with stirring at 2000 rpm for 10 minutes at room temperature and then defoamed at 2200 rpm for 1 minute using a stirrer (Awatori Nertaro (registered trademark) ARE-250 manufactured by THINKY). Carry out the liquid It was obtained EPDM adhesive D.

<Manufacture of adhesives>
In the production of the adhesive body of Example 1, instead of the adhesive A, the liquid EPDM adhesive D obtained above was used, and the bonding / crosslinking conditions were set to a pressure of 1 MPa, a temperature of 150 ° C., and a time of 10 minutes. In the same manner, an adhesive body as a laminate was obtained.
The evaluation results are shown in Table 1.
[Example 5]

<Production of ethylene / propylene / ENB / VNB copolymer (A-3)>
A quaternary copolymer consisting of ethylene, propylene, 5-ethylidene-2-norbornene (ENB) and component 5-vinyl-2-norbornene (VNB) continuously using a 300 L capacity polymerization vessel equipped with a stirring blade The polymerization reaction was carried out at 95 ° C.

As a polymerization solvent, hexane (feed amount 41 kg / h) was used, ethylene feed amount 5.3 kg / h, propylene feed amount 5.6 kg / h, ENB feed amount 900 g / h, VNB feed amount 90 g / h. h was continuously fed to the polymerization vessel. Using (t-butylamido) dimethyl (η5-2-methyl-s-indasen-1-yl) silanetitanium (II) 1,3-pentadiene as the main catalyst while maintaining the polymerization pressure at 1.5 MPa, 0. The polymerization vessel was continuously fed so as to be 05 mmol / h. In addition, each of the polymerizers was such that (C ₆ H ₅ ) ₃ CB (C ₆ F ₅ ) ₄ was 0.25 mmol / h as a cocatalyst and triisobutylaluminum (TIBA) was ₁₅ mmol / h as an organoaluminum compound. Continuously fed.

  In this way, a polymerization liquid containing 16.6% by weight of a copolymer composed of ethylene, propylene, ENB and VNB was obtained. A small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction, and the polymer was separated from the solvent by a steam stripping treatment, and then dried under reduced pressure at 80 ° C. for a whole day and night. An ENB / VNB copolymer (A-3) was obtained.

  The obtained copolymer (A-3) contains 56.1 mol% of ethylene and 41.2 mol% of α-olefin (propylene) in 100 mol% of the copolymer, and has an iodine value of 1.42 [ g / 100 g], intrinsic viscosity [η] was 1.59, Mn = 38,000, and it was solid at room temperature (viscosity at 25 ° C. exceeds 5,000 Pa · s).

<Preparation of adhesive>
100 parts by weight of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1) obtained in Example 1 and the ethylene / propylene / ENB / VNB copolymer (A-3) obtained above. ) 50 parts by weight and 175 parts by weight of a plasticizer (Linearene 12, manufactured by Idemitsu Kosan Co., Ltd.) whose main component is α-olefin (C12) where n = 4 in the following chemical formula (1); 9 parts by weight of oxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (trade name: Kayahexa AD, manufactured by Kayaku Akzo) and triallyl isocyanurate (TAIC) as a crosslinking aid (Registered Trademark, manufactured by Nippon Kasei Co., Ltd.) 1 part by weight, using a stirrer (manufactured by THINKY Co., Ltd. Awatori Neritaro (Registered Trademark) ARE-250) at room temperature and 10 rpm. Stir for minutes Mixed Te, then performing one minute defoamed 2200 rpm, to obtain a liquid EPDM adhesive E.

<Manufacture of adhesives>
In the production of the adhesive body of Example 1, an adhesive body as a laminate was obtained in the same manner except that the liquid EPDM adhesive E obtained above was used instead of the adhesive A.
The evaluation results are shown in Table 1.

[Comparative Example 1]
<Preparation of adhesive>
100 parts by weight of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer (A-1) obtained in Example 1 and 2,5-dimethyl-2,5- 3 parts by weight of di (t-butylperoxy) hexane (trade name: Kayahexa AD, manufactured by Kayaku Akzo Co., Ltd.) and a stirrer (manufactured by THINKY Co., Ltd., Awatori Neritaro (registered trademark) ARE-250) ) And stirred at 2000 rpm for 10 minutes at room temperature and then defoamed at 2200 rpm for 1 minute to obtain a liquid EPDM adhesive F.

<Manufacture of adhesives>
In the production of the adhesive body of Example 1, an adhesive body as a laminate was obtained in the same manner except that the liquid EPDM adhesive F obtained above was used instead of the adhesive A.
The evaluation results are shown in Table 1.

[Comparative Example 2]
<Manufacture of adhesives>
As the adherend, two EPDM molded sheets (50 mm × 50 mm, thickness 2 mm) formed by carbon-containing sulfur vulcanization, the same as those used in Example 1, were prepared. 1 g of EPDM molded sheet was coated with 1 g of chloroprene rubber dissolved in a toluene solvent in a solid content of 20% by weight as adhesive G, dried, and then another EPDM molded sheet (adhesive) (No application) was laminated together. This was crosslinked under the conditions of a pressure of 1 MPa, a temperature of 170 ° C., and a time of 30 minutes to obtain an adhesive body as a laminate.
The evaluation results are shown in Table 1.

  The rubber bonded body of the present invention obtained by using the adhesive according to the present invention is a composite in which a rubber molded body and other materials, or rubber molded bodies are bonded to each other. Can be used without limitation. For example, it can be suitably used for automobile interior and exterior products, aircraft / ship materials, building materials, electrical appliances, office equipment, household items, sealing, packing, and the like.

Claims (22)

A rubber bonded body formed by contacting an adherend (1) which is a rubber molded body, a layer formed by crosslinking the adhesive (X), and an adherend (2) which is a molded body made of rubber or other materials. Because
The adhesive (X) has an ethylene / α-olefin / polyene copolymer (A) having a viscosity at 25 ° C. of 1 Pa · s or more and less than 5,000 Pa · s, and the following (B-1 ), (B-2) and (B-3) and at least one crosslinking agent (B) selected from the group consisting of (B-3);
(B-1) Organic peroxide and allyl compound-based crosslinking aid,
(B-2) a sulfur compound,
(B-3) SiH group-containing compound.   The polyene of the ethylene / α-olefin / polyene copolymer (A) is at least one selected from 1,3-butadiene, isoprene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene. The rubber adhesive body according to claim 1, wherein   The rubber adhesive according to claim 1 or 2, wherein the crosslinking agent (B) is (B-1) an organic peroxide and an allyl compound-based crosslinking aid. The crosslinking agent (B) is an organic peroxide described in the following general formula (a) and / or the following general formula (b), and allyl represented by the following formula (c) and / or the following formula (d). The rubber adhesive according to claim 1, further comprising a compound-based crosslinking aid.
X ¹ —O—O—X ² —O—O—X ³ (a)
(In formula (a), X ¹ , X ² and X ³ each independently represents an organic group having 4 or more carbon atoms)
Y ¹ —O—O—Y ² (b)
(In formula (b), Y ₁ and Y ₂ each independently represents an organic group having 4 or more carbon atoms)

  The intrinsic viscosity [η] of the ethylene / α-olefin / polyene copolymer (A) measured with a decalin solution at 135 ° C. is in the range of 0.01 to 0.50 (dl / g). The rubber adhesive body in any one of -4.   The rubber adhesive according to any one of claims 1 to 5, wherein the ethylene / α-olefin / polyene copolymer (A) is an ethylene / α-olefin / non-conjugated polyene.   The rubber adhesive according to any one of claims 1 to 5, wherein the ethylene / α-olefin / polyene copolymer (A) is ethylene / propylene / non-conjugated polyene.   The rubber adhesive according to any one of claims 1 to 5, wherein the ethylene / α-olefin / polyene copolymer (A) is ethylene / propylene / 5-vinyl-2-norbornene.   The rubber adhesive according to any one of claims 1 to 8, wherein the adhesive (X) does not substantially contain a solvent.   At least one of the adherend (1) and the adherend (2) is a crosslinked rubber molded article obtained using at least one selected from a sulfur-based compound and an organic peroxide as a crosslinking agent. The rubber bonded body according to any one of claims 1 to 9.   The rubber adherend according to any one of claims 1 to 10, wherein the adherend (1) and the adherend (2) are sheet-like crosslinked rubber molded bodies. On the adhesion surface of the adherend (1), which is a rubber molded body, and / or the adhesion surface of the adherend (2), which is a molded body made of rubber or other material,
An ethylene / α-olefin / polyene copolymer (A) having a viscosity at 25 ° C. of 1 Pa · s or more and less than 5,000 Pa · s, the following (B-1), (B-2) and Applying an adhesive (X) containing at least one crosslinking agent (B) selected from the group consisting of (B-3);
Bonding the adhesion surfaces of the adherend (1) and the adherend (2) through the applied adhesive (X);
A method for producing a rubber bonded body comprising a step of crosslinking the adhesive (X);
(B-1) Organic peroxide and allyl compound-based crosslinking aid,
(B-2) a sulfur compound,
(B-3) SiH group-containing compound. An ethylene / α-olefin / polyene copolymer (A) having a viscosity at 25 ° C. of 1 Pa · s or more and less than 5,000 Pa · s;
An adhesive (X) for producing a rubber bonded body comprising at least one crosslinking agent (B) selected from the group consisting of the following (B-1), (B-2) and (B-3) ;
(B-1) Organic peroxide and allyl compound-based crosslinking aid,
(B-2) a sulfur compound,
(B-3) SiH group-containing compound.   The polyene of the ethylene / α-olefin / polyene copolymer (A) is at least one selected from 1,3-butadiene, isoprene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene. The adhesive (X) for producing a rubber bonded body according to claim 13, wherein the adhesive is an adhesive.   The adhesive (X) for producing a rubber bonded body according to claim 13 or 14, wherein the crosslinking agent (B) is (B-1) an organic peroxide and an allyl compound-based crosslinking aid. The crosslinking agent (B) is an organic peroxide described in the following general formula (a) and / or the following general formula (b), and allyl represented by the following formula (c) and / or the following formula (d). The adhesive (X) for producing a rubber bonded body according to any one of claims 13 to 15, comprising a compound-based crosslinking aid.
X ¹ —O—O—X ² —O—O—X ³ (a)
(In formula (a), X ¹ , X ² and X ³ each independently represents an organic group having 4 or more carbon atoms)
Y ¹ —O—O—Y ² (b)
(In formula (b), Y ₁ and Y ₂ each independently represents an organic group having 4 or more carbon atoms)

  The ethylene / α-olefin / polyene copolymer (A) has an intrinsic viscosity [η] measured with a decalin solution at 135 ° C. in a range of 0.01 to 0.50 (dl / g). The adhesive (X) for manufacturing a rubber bonded body according to any one of claims 13 to 16.   The adhesive for producing a rubber adhesive according to any one of claims 13 to 17, wherein the ethylene / α-olefin / polyene copolymer (A) is an ethylene / α-olefin / non-conjugated polyene. X).   The adhesive (X) for producing a rubber bonded body according to any one of claims 13 to 17, wherein the ethylene / α-olefin / polyene copolymer (A) is ethylene / propylene / non-conjugated polyene. .   18. The adhesive for producing a rubber bonded body according to claim 13, wherein the ethylene / α-olefin / polyene copolymer (A) is ethylene / propylene / 5-vinyl-2-norbornene. Agent (X).   The adhesive (X) for producing a rubber bonded body according to any one of claims 13 to 20, which is substantially free of a solvent.   The adhesive (X) for producing a rubber bonded body according to any one of claims 13 to 21, which is used for bonding a crosslinked rubber molded body.