JP2005298592A - Adhesive rubber composition and adhesive rubber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive rubber excellent in resistance to blooming, resistance to environmental deterioration, resistance to sealing, and resistance to offensive smell, having a short crosslinking and adhering time, and suitable for adhesion to a rubber which is obtained by crosslinking other than sulfur vulcanization. <P>SOLUTION: The subject adhesive rubber composition of millable type comprises (A) an ethylene-α-olefin-nonconjugated polyene random copolymer rubber having structural units derived from at least one kind of specific nonconjugated polyene, (B) an SiH radical-containing compound having at least two SiH radicals in its molecule, and (C) a catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an adhesive composition and an adhesive member. More specifically, the present invention is suitable for adhesion to a crosslinked rubber obtained by a method other than sulfur vulcanization, rubber elasticity, flexibility, weather resistance, water resistance, and heat resistance. Adhesive rubber composition with excellent aging, cold resistance, seal resistance, adhesiveness, environmental safety and hygiene, odor resistance, bloom resistance, excellent fluidity during molding, and short molding cycle And an adhesive rubber obtained from the composition.

Conventionally, silicone adhesives and urethane adhesives have been used as adhesive rubber compositions with excellent flexibility, but all of them are liquid types and are generally made for millable types. It has been difficult to use in general extruders, press molding machines, injection molding machines, and transfer molding machines.
WO01 / 98407 Therefore, millable type rubber compositions and the like are used.

  For example, automotive weather strip material is generally used by injecting a millable type EPDM composition between straight rubber and straight rubber that have been extrusion-crosslinked by injection molding using an injection molding machine or press molding machine. It is manufactured.

  However, adhesive rubbers made from commonly used EPDM compositions have the advantages of blooming vulcanizing agents and accelerators, environmental hygiene, and environmental degradation resistance (weather resistance, heat aging resistance). There is a need for improvement. In addition, because weather strip materials for automobiles are used as seal materials for doors and trunks, they have high seal performance to prevent water and dust from entering from outside, and unpleasant odors for people in the vehicle. However, an adhesive rubber made from a generally used EPDM composition is required to be improved in terms of seal performance and odor resistance. Furthermore, the vulcanization adhesion time of the adhesive rubber is long and the molding cost is high.

  Therefore, it is a millable type that can be used in general molding, and has excellent bloom resistance, environmental hygiene resistance (weather resistance, heat aging resistance), environmental degradation resistance, seal resistance, and odor resistance. Therefore, a material that can shorten the cross-linking adhesion time and can maintain the flexibility, water resistance, cold resistance, and adhesion properties of conventional EPDM is desired. In addition, as the adherend, rubber cross-linked by the method of sulfur vulcanization and rubber cross-linked by a method other than sulfur vulcanization may have different uses and purposes, and when using adhesive rubber The property of selectively adhering to rubber crosslinked by a method other than sulfur vulcanization is preferable. If such properties are achieved, a rubber cross-linked by a method of sulfur vulcanization as an adherend and a rubber cross-linked by a method other than sulfur vulcanization are mistaken at the production site of a rubber molded body. The rubber that has been selectively cross-linked by a method other than sulfur vulcanization can be bonded with an adhesive rubber, and errors in the manufacturing process are reduced.

Patent Document 2 below discloses a crosslinkable rubber composition having a high crosslinking rate and capable of hot air crosslinking, and excellent in compression set resistance, strength characteristics, heat resistance, weather resistance, and wear resistance. ing. However, there is no description about a rubber for adhesion with a specific crosslinked rubber.
JP2001-049057

  The problems to be solved are that conventional EPDM compositions have poor resistance to bloom, environmental hygiene, environmental degradation, seal resistance and odor resistance, and a long cross-linking adhesion time. . It is another object of the present invention to provide an adhesive rubber that is suitable for adhesion to a rubber that has been crosslinked by a method other than sulfur vulcanization.

  The rubber composition for adhesion of the present invention is an ethylene / α-olefin / nonconjugated polyene random copolymer rubber having a structural unit derived from at least one nonconjugated polyene represented by the following general formula [I] or [II] It is characterized by being a millable type comprising (A), a SiH group-containing compound (B) having at least two SiH groups in one molecule, and a catalyst (C). Here, the millable type is contrasted with the liquid type and indicates a viscosity that can be processed using a normal rubber processing machine. For example, refer to the rubber glossary; Japan Rubber Association, 1997).

[Wherein 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] ,

[Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms].

  The adhesive member of the present invention is obtained from the adhesive rubber composition.

  Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) having a structural unit derived from at least one non-conjugated polyene represented by the general formula [I] or [II], and one molecule of SiH group By using a millable adhesive rubber composition comprising at least two SiH group-containing compounds (B) and a catalyst (C), it can be used in general molding, and further has a resistance to bloom. , Environmental hygiene resistance (weather resistance, heat aging resistance), environmental degradation resistance, seal resistance, odor resistance, crosslink adhesion time can be shortened, and flexibility, water resistance, Maintains cold resistance and adhesion. Moreover, the rubber | gum made from the EPDM composition which used the sulfur generally used conventionally as a vulcanizing agent may bloom a vulcanizing agent and a vulcanization accelerator. In addition, although the environmental degradation resistance (weather resistance, heat aging resistance), seal performance, and odor resistance may not be sufficient, the adhesive rubber of the present invention is used with a crosslinked rubber obtained by sulfur vulcanization. Since the adhesiveness is low, it is possible to prevent these rubbers from being mistakenly bonded to make a product, and to selectively adhere to a crosslinked rubber obtained by a method other than sulfur vulcanization, which is superior in these properties. .

[Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A)]
The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention is composed of ethylene, an α-olefin having 3 to 20 carbon atoms, and the general formula [I] or [II]. It is a random copolymer with the nonconjugated polyene represented.

  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 and 1-nonene. 1-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-1-dodecene, 12-ethyl-1-tetradecene and the like. Among these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used. These α-olefins are used alone or in combination of two or more.

  The non-conjugated polyene used in the present invention is a terminal vinyl group-containing norbornene compound represented by the following general formula [I] or [II].

In the general 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 the alkyl group having 1 to 10 carbon atoms of R ¹ is Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, t-pentyl group, neopentyl group Hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.

R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms of R ² include alkyl groups having 1 to 5 carbon atoms among the specific examples of R ¹ described above.

In the general formula [II], R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group for R ³ include the same alkyl groups as the specific examples of the alkyl group for R ¹ .

  Specific examples of the non-conjugated polyene represented by the general formula [I] or [II] include 5-methylene-2-norbornene, 5-vinyl-2-norbornene, and 5- (2-propenyl) -2- Norbornene, 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- (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-norbo Nene, 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-hexenyl) -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- (6-heptenyl) -2-norbornene and 5- (7-octenyl) -2-norbornene are preferred. These norbornene compounds can be used alone or in combination of two or more.

  In addition to the non-conjugated polyene such as 5-vinyl-2-norbornene, the following non-conjugated polyene may be used in combination as long as the physical properties of the present invention are not impaired.

  Specific examples of such a non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, Chain non-conjugated dienes such as 4,5-dimethyl-1,4-hexadiene and 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5 -Cyclic non-conjugated dienes such as isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, dicyclopentadiene; 2,3-diisopropylidene-5 Norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norborna Such as trienes such as ene.

  The ethylene / α-olefin / non-conjugated polyene random copolymer (A) comprising the above components is preferably any one or more of the following properties (i) to (v), preferably the properties: (I) to (iv) are all included.

(I) Molar ratio of ethylene and α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin)
The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is composed of (a) a unit derived from ethylene and (b) an α-olefin having 3 to 20 carbon atoms (hereinafter simply referred to as “α-olefin”). The unit derived from (A) is usually 50/50 to 90/10, preferably 60/40 to 90/10, preferably 65/35 to 85/15, particularly preferably 65/35 to 80/20 moles. It is contained at a ratio [(a) / (b)].
When this molar ratio is within the above range, a rubber composition capable of providing an adhesive rubber excellent in rubber elasticity, flexibility, weather resistance, heat aging resistance, seal resistance, strength characteristics, and cold resistance can be obtained. Thus, an adhesive rubber composition excellent in kneading processability and roll processability in a closed mixer can be obtained.

(Ii) Iodine value The iodine value of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is usually 1 to 30 (g / 100 g), preferably 1 to 25 (g / 100 g), more preferably. Is 2 to 20 (g / 100 g), particularly preferably 2 to 10 (g / 100 g), and most preferably 2 to 6 (g / 100 g).
When the iodine value is within the above range, a rubber composition capable of providing an adhesive rubber excellent in rubber elasticity, flexibility, weather resistance, heat aging resistance, and seal resistance is obtained, and excellent in adhesiveness. An adhesive rubber composition is obtained. Further, if the iodine value is 30 or less, it is more advantageous in terms of cost.

(Iii) Intrinsic viscosity The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) measured in decalin at 135 ° C. is preferably 0.95 to 4 dl / g, more preferably It is desirable to be 1.0 to 3 dl / g, particularly preferably 1.0 to 2 dl / g, and most preferably 1.0 to 1.8.
When this intrinsic viscosity [η] is within the above range, a rubber composition capable of providing an adhesive rubber excellent in rubber elasticity and strength properties can be obtained, and also excellent in adhesiveness and roll processability, press molding and injection An adhesive rubber composition having excellent fluidity during molding and transfer molding can be obtained.

(Iv) Branching index The branching index determined from the dynamic viscoelasticity measuring device of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is preferably 3 to 20, more preferably 5 to 20, Preferably it is 7-20. If the value of this branching index is 3 or more, the viscosity in the low shear rate region is not low, and the rubber composition for adhesion does not become sticky. Therefore, the handling properties during press molding, injection molding, and transfer molding are good. Therefore, it is preferable. Moreover, if it is 20 or less, the elongation characteristic at the time of a tensile fracture is especially favorable, and since adhesive strength is higher, it is preferable.

(V) Polyene content The polyene content of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is usually 0.01 to 25 (wt%), preferably 0.1 to 10 (wt%), More preferably, it is 0.2-5 (wt%), Especially preferably, it is 0.5-3 (wt%), Most preferably, it is 1-3 (wt%).

  The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention has the following physical properties (vi) in addition to the physical properties (i) to (v). It is preferable.

(Vi) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) measured by GPC is usually 2 to 200, preferably 5 to 150, more preferably 10 to 120, and particularly Preferably it is 10-100. If the molecular weight distribution is 2 or more, the fluidity is improved, and the wettability with the adherend rubber is improved, so that the adhesiveness is improved. On the other hand, a molecular weight distribution of 200 or less is preferable in terms of adhesive strength, rubber elasticity, and seal resistance.

  The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention is a polymer production process (Industrial Research Committee, published on pages 309 to 330) or the applicant's application. JP-A-9-71617, JP-A-9-71618, JP-A-9-208615, JP-A-10-67823, JP-A-10-67824, JP-A-10-110054, etc. It can be prepared by a conventionally known method as described.

  Examples of the olefin polymerization catalyst used in the production of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention include vanadium (V), zirconium (Zr), and titanium (Ti). Ziegler catalyst comprising a transition metal compound such as an organoaluminum compound (organoaluminum oxy compound), or a metallocene compound of a transition metal selected from Group IVB of the periodic table of elements, an organoaluminum oxy compound or an ionized ionic compound A metallocene catalyst consisting of is particularly preferably used.

  When the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is prepared using a catalyst containing the following compounds (H) and (I) as main components, the boiling xylene insoluble content is 1 % Or less of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is preferable.

That is, the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) having an xylene insoluble content of 1% or less is present in the presence of a catalyst containing the following compounds (H) and (I) as main components. , Polymerization temperature 30 to 60 ° C., especially 30 to 59 ° C., polymerization pressure 4 to 12 kgf / cm ² , particularly 5 to 8 kgf / cm ² , molar ratio of supply amount of non-conjugated polyene and ethylene (non-conjugated polyene / ethylene) By randomly copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene represented by the above general formula [I] or [II] under the condition of 0.01 to 0.2. can get. The copolymerization is preferably carried out in a hydrocarbon medium.
(H) a soluble vanadium compound represented by VO (OR) _y X _3-y (wherein R is a hydrocarbon group, X is a halogen atom, and y is an integer of 0 or 1 to 3), Or a vanadium compound represented by VX ₄ (X is a halogen atom).

The soluble vanadium compound (H) is a component that is soluble in the hydrocarbon medium of the polymerization reaction system. Specifically, the general formula VO (OR) _a X _b or V (OR) _c X _d (wherein R Is a hydrocarbon group, represented by 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4), or These electron donor adducts can be given as typical examples.

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 (On-C ₄ H ₉ ) ₃ , VCl ₃ · 2OC ₆ H ₁₂ OH, etc. be able to.
(I) An organoaluminum compound represented by R ′ _z AlX′3- _z (R ′ is a hydrocarbon group, X ′ is a halogen atom, and z is an integer of 1 to 3).

Specific examples of the organoaluminum compound (I) include trialkylaluminum such as triethylaluminum, tributylaluminum, and triisopropylaluminum; dialkylaluminum alkoxide 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, etc .; diethylaluminum chloride, dibutylaluminum chloride, Dialkylaluminum halides such as diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum Alkyl aluminum sesquihalides such as skichloride, 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 dialkylaluminum hydrides such as diethylaluminum hydride, ethylaluminum dihydride, propylaluminum dihydride, etc .; moieties such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclide, ethylaluminum ethoxybromide Alkoxylated and halogenated alkylal Or the like can be mentioned chloride.

In the present invention, among the above compound (H), a soluble vanadium compound represented by VOCl ₃ and among the above compound (I), Al (OC ₂ H ₅ ) ₂ Cl / Al ₂ (OC ₂ H ₅ ) ₃ Cl _When the blended product with No. ₃ (blend ratio is 1/5 or more) is used as a catalyst component, the insoluble content after Soxhlet extraction (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) is 1% or less. Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is preferable because it is obtained.

[SiH group-containing compound (B)]
The SiH group-containing compound (B) used in the present invention reacts with the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) and acts as a crosslinking agent. The molecular structure of the SiH group-containing compound (B) is not particularly limited, and it can be used for conventionally produced resinous materials such as linear, cyclic, branched structures, or three-dimensional network structures. 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.

Such SiH group-containing compound (B) is usually represented by the following general composition formula R ⁴ _b H _c SiO _{(4-bc) / 2}
The compound represented by these can be used.

In the above general composition formula, R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, excluding an aliphatic unsaturated bond. Examples of the valent hydrocarbon group include a phenyl group and a halogen-substituted alkyl group such as a trifluoropropyl group in addition to the alkyl group exemplified for R1. 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.

  Further, 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.

This SiH group-containing compound (B) is an organohydrogenpolysiloxane having preferably 2 to 1000, particularly preferably 2 to 300, and most preferably 4 to 200 silicon atoms in one molecule. Specifically, siloxane oligomers such as 1,3,5,7-tetramethyltetracyclosiloxane, 1,3,5,7,8-pentamethylpentacyclosiloxane, etc .; Siloxane, molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both ends silanol group-blocked methylhydrogenpolysiloxane, molecular chain both ends silanol group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer Combined, dimethyl at both ends of molecular chain Idro blocked with dimethylhydrogensiloxy groups at both molecular chain terminals with dimethylhydrogensiloxy groups methylhydrogenpolysiloxane capped at both molecular chain terminals blocked with dimethylhydrogensiloxy groups dimethylsiloxane-methylhydrogensiloxane copolymer, R ⁴ ₂ ( H) composed of 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, (H ) Silicone resins that may contain SiO _3/2 or R ⁴ SiO _3/2 units.

  Examples of the methyl hydrogen polysiloxane blocked with a trimethylsiloxy group at both ends of the molecular chain include, for example, a compound represented by the following formula, and further, in the following formula, a part or all of the methyl group is an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group. And the like.

(a) (CH ₃ ) ₃ SiO — (— SiH (CH ₃ ) —O—) _d —Si (CH ₃ ) ₃
[D in the formula is an integer of 2 or more. ]
As the dimethylsiloxane / methylhydrogensiloxane copolymer blocked with trimethylsiloxy group at both ends of the molecular chain, a compound represented by the following formula, and further, in the following formula, part or all of the methyl group is ethyl group, propyl group, phenyl group, Examples include compounds substituted with a trifluoropropyl group and the like.

_{(b) (CH 3) 3} SiO - (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f- Si (CH 3) 3
[In the formula, e is an integer of 1 or more, and f is an integer of 2 or more. ]
Examples of the methyl hydrogen polysiloxane blocked with silanol groups at both ends of the molecular chain include, for example, a compound represented by the following formula, and a part or all of the methyl group in the following formula: ethyl group, propyl group, phenyl group, trifluoropropyl group, etc. And the like.

_{(c) HOSi (CH 3)} 2 O - (- SiH (CH 3) -O-) 2 -Si (CH 3) 2 OH
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 formula, and further a part or all of the methyl group in the following formula: an ethyl group, a propyl group, a phenyl group, Examples include compounds substituted with a trifluoropropyl group and the like.

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

(e) HSi (CH ₃ ) ₂ O — (— Si (CH ₃ ) ₂ —O—) _e —Si (CH ₃ ) ₂ H
[E in the formula is an integer of 2 or more. ]
Examples of the methyl hydrogen polysiloxane blocked with dimethylhydrogensiloxy group blocked at both ends of the molecular chain include, for example, a compound represented by the following formula, and further a part or all of the methyl group in the following formula: ethyl group, propyl group, phenyl group, trifluoro Examples thereof include compounds substituted with a propyl group or the like.

(f) HSi (CH ₃ ) ₂ O — (— SiH (CH ₃ ) —O—) _e —Si (CH ₃ ) ₂ H
[E in the formula is an integer of 2 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 formula, and further a part or all of the methyl group in the following formula: ethyl group, propyl group, And compounds substituted with a phenyl group, a trifluoropropyl group, and the like.

(g) HSi (CH ₃ ) ₂ O — (— Si (CH _{3) 2} —O—) _e — (— SiH (CH ₃ ) —O—) _h —Si (CH ₃ ) ₂ H [e And h are each an integer of 1 or more. ]
Such a compound can be produced by a known method, for example, octamethylcyclotetrasiloxane and / or tetramethylcyclotetrasiloxane and hexamethyldisiloxane or 1,3-dihydro-1,1 which can be a terminal group. , 3,3-tetramethyldisiloxane and other compounds containing a triorganosilyl group or a diorganohydrogensiloxy group in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid, methanesulfonic acid, etc. It can be easily obtained by equilibrating at a temperature of about ~ 40 ° C.

Examples of the SiH-containing compound also include compounds represented by the following general formula.
(R ⁴ ) _m -Si-[-O- (Si (CH ₃ ) ₂ -O-) _n -Si (CH ₃ ) ₂ H] _{4 -m}
In the above general formula, R ⁴ has the same meaning as R ⁴ described above. M is 0 or 1, and n is an integer of 0-10. Further it can be mentioned in the general formula each CH ₃ group each independently an ethyl group, a propyl group, and compounds obtained by replacing the phenyl group.

  The SiH group-containing compound (B) is usually 0.1 to 100 parts by weight, preferably 0.1 to 75 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). Parts, more preferably 0.1 to 50 parts by weight, still more preferably 0.2 to 30 parts by weight, even more preferably 0.2 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, most preferably It is used at a ratio of 0.5 to 5 parts by weight. When the SiH group-containing compound (B) is used in a proportion within the above range, the rubber elasticity, flexibility, water resistance, adhesiveness, bloom resistance, and cold resistance are excellent, the crosslinking density is moderate, the strength characteristics and the elongation are excellent. An adhesive rubber composition capable of forming a crosslinked rubber molded article having excellent characteristics is obtained. Use of the SiH group-containing compound (B) in a proportion of 100 parts by weight or less is more advantageous in terms of cost.

The SiH-containing compound preferably has no SiH group at the molecular end from the viewpoint of adhesiveness. For example, the compounds (a) to (d) in the above examples are more preferable. Here SiH group at a molecular terminal and does not exist, for example, ^{Si A -O-Si B -O-} Si C as -O-Si ^D Assuming that there are compounds, also Si ^A, hydrogen in Si ^D Indicates that they are not joined.

[Catalyst (C)]
The catalyst (C) used in the present invention is an addition reaction catalyst, and the alkenyl group of the ethylene / α-olefin / nonconjugated polyene random copolymer rubber (A) component and the SiH group-containing compound (B) SiH. There is no particular limitation as long as it promotes an addition reaction with a group (hydrosilylation reaction of an alkene). For example, an addition reaction catalyst (periodic table) composed of a platinum group element such as a platinum catalyst, a palladium catalyst, a rhodium catalyst, etc. Group 8 metal catalysts such as Group 8 metals, Group 8 metal complexes, Group 8 metal compounds, etc.), among which platinum catalysts are preferred.

  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, platinum alone (platinum black), chloroplatinic acid, platinum-olefin complex, platinum-alcohol complex, platinum-siloxane complex, or a carrier in which platinum carrier is supported on alumina, silica, etc. Is mentioned.

  The palladium-based catalyst is composed of palladium, a palladium compound, palladium chloride acid, and the like, and the rhodium-based catalyst is composed of rhodium, rhodium compound, rhodium chloride acid, and the like.

  Examples of the catalyst (C) other than the above include Lewis acid and cobalt carbonyl. The catalyst (C) is 0.1 to 100,000 ppm by weight, preferably 0.1 to 10,000 ppm by weight, based on the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). Preferably it is used in a proportion of 1 to 5,000 ppm by weight, particularly preferably 5 to 1,000 ppm by weight.

  When the catalyst (C) is used in a proportion within the above range, a rubber composition capable of forming a crosslinked rubber molded article having a moderate crosslinking density and excellent strength properties and elongation properties can be obtained, and adhesion having excellent adhesion and crosslinking speed can be obtained. A rubber composition is obtained. Use of the catalyst (C) in a proportion exceeding 100,000 ppm by weight is not preferable because it is disadvantageous in terms of cost.

  In the present invention, an uncrosslinked rubber molded body of the rubber composition not containing the catalyst (C) can be irradiated with light, γ rays, electron beams, etc. to obtain a crosslinked rubber molded body.

[Reaction inhibitor (D)]
Examples of the reaction inhibitor (D) used as an optional component together with the catalyst (C) in the present invention include benzotriazole, ethynyl group-containing alcohols (for example, ethynylcyclohexanol), acrylonitrile, amide compounds (for example, N, N-diallylacetamide, N, N-diallylbenzamide, N, N, N ′, N′-tetraallyl-o-phthalic acid diamide, N, N, N ′, N′-tetraallyl-m-phthalic acid diamide, N, N, N ′, Organic peroxides such as N'-tetraallyl-p-phthalic acid diamide), sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, tetramethyltetravinylcyclotetrasiloxane, hydroperoxide Etc.

  The reaction inhibitor (D) is 0 to 50 parts by weight, usually 0.0001 to 50 parts by weight, preferably 0 with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). 0.0001 to 30 parts by weight, more preferably 0.0001 to 20 parts by weight, still more preferably 0.0001 to 10 parts by weight, and particularly preferably 0.0001 to 5 parts by weight.

  When the reaction inhibitor (D) is used in a proportion of 50 parts by weight or less, an adhesive rubber composition having an excellent balance of adhesion, scoring resistance and crosslinking speed can be obtained. If the reaction inhibitor (D) is used in a proportion exceeding 50 parts by weight, it is not preferable because it is disadvantageous in terms of cost.

  The adhesive rubber composition of the present invention comprises the component (A), the component (B), and the component (C) as described above, and the component (D) may further exist as necessary. Furthermore, the following components can be used as needed.

  In the adhesive rubber composition according to the present invention, a conventionally known rubber reinforcing agent, inorganic filler, softener, anti-aging agent, processing aid, vulcanization accelerator, depending on the intended use of the crosslinked product, etc. Additives such as organic peroxides, crosslinking aids, foaming agents, foaming aids, colorants, dispersants, flame retardants, and the like can be blended within a range that does not impair the object of the present invention. Among these, those that do not inhibit the hydrosilylation reaction of the alkene are preferable.

  The rubber reinforcing agent has an effect of improving mechanical properties such as tensile strength, tear strength, and wear resistance of the crosslinked rubber. Specific examples of such rubber reinforcing agents include carbons such as SRF, GPF, FEF, HAF, ISAF, SAF, FT, and MT, and those carbons that have been surface-treated with a silane coupling agent. Examples thereof include black, finely divided silicic acid, and silica.

Specific examples of silica include fumed silica and precipitated silica. These silicas may be surface-treated with a reactive silane such as hexamethyldisilazane, chlorosilane, or alkoxysilane, or a low molecular weight siloxane.
The specific surface area of silica (BED method) is preferably 50 m ² / g or more, more preferably 100 to 400 m ² / g.

  The type and blending amount of these rubber reinforcing agents can be appropriately selected depending on the application, but the blending amount of the rubber reinforcing agent is usually at most 300 parts by weight, preferably at most, with respect to 100 parts by weight of the organic polymer (A). 200 parts by weight.

  Specific examples of the inorganic filler include light calcium carbonate, heavy calcium carbonate, talc, and clay.

Although the kind and compounding quantity of these inorganic fillers can be suitably selected according to the application, the compounding quantity of the inorganic filler is usually 300 parts by weight at the maximum with respect to 100 parts by weight of the organic polymer (A), preferably the maximum. 200 parts by weight.
As the softener, a softener usually used for rubber can be used.

Specifically, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly;
Coal tar softeners such as coal tar and coal tar pitch;
Fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, coconut oil;
Tall oil;
sub;
Waxes such as beeswax, carnauba wax, lanolin;
Fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate, zinc laurate;
Examples thereof include synthetic polymer materials such as petroleum resins, atactic polypropylene, and coumarone indene resins. Of these, petroleum softeners are preferably used, and process oil is particularly preferably used.
The blending amount of these softeners is appropriately selected depending on the use of the crosslinked product.

  Examples of the anti-aging agent include amine-based, hindered phenol-based, and sulfur-based anti-aging agents. These anti-aging agents are used within the range not impairing the object of the present invention as described above. It is done.

  Examples of amine-based antioxidants used in the present invention include diphenylamines and phenylenediamines.

There are no particular restrictions on the type of amine-based antioxidant used, but 4,4 ′-(α, α-dimethylbenzyl) diphenylamine and N, N′-di-2-naphthyl-p-phenylenediamine are preferred.
These compounds can be used alone or in combination of two or more.

The hindered phenol-based anti-aging agent used in the present invention is not particularly limited, and for example, (1) tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′- Hydroxyphenyl) propionate methane,
(2) 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4-8,10- Preferred examples include tetraoxaspiro [5,5] undecane (3) 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol).

  As the sulfur-based anti-aging agent used in the present invention, a sulfur-based anti-aging agent usually used for rubber is used.

  There are no particular restrictions on the sulfur-based antioxidant used, but in particular 2-mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, pentaerythritol- Tetrakis- (β-lauryl-thiopropionate) is preferred.

  As said processing aid, the compound used for processing of a normal rubber can be used. Specifically, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid and lauric acid; salts of higher fatty acids such as barium stearate, zinc stearate and calcium stearate; ricinoleic acid, stearic acid, palmitic acid and lauric acid And higher fatty acid esters.

  Such a processing aid is usually used in a proportion of 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the organic polymer (A). It is desirable to determine the optimal amount.

In the present invention, in addition to the catalyst (C) described above, an organic peroxide may be used to perform both addition crosslinking and radical crosslinking. The organic peroxide is used at a ratio of about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). As the organic peroxide, a conventionally known organic peroxide that is usually used in crosslinking of rubber can be used.
Moreover, when using an organic peroxide, it is preferable to use a crosslinking aid in combination. Specific examples of the crosslinking aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; maleimide Compounds such as divinylbenzene. Such a crosslinking aid is used in an amount of 0.5 to 2 mol, preferably about equimolar to 1 mol of the organic peroxide used.

  Further, the rubber composition for bonding according to the present invention can be used by blending with other known rubbers within a range not impairing the object of the present invention. Examples of such other rubber include natural rubber (NR) and isoprene rubber (IR), isoprene-based rubber, butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and chloroprene rubber. Mention may be made of conjugated diene rubbers such as (CR).

  Further, conventionally known ethylene / α-olefin copolymer rubbers can also be used. For example, ethylene / propylene random copolymer (EPR), ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). Other ethylene / α-olefin / polyene copolymers (for example, EPDM) can be used.

  The adhesive member according to the present invention is obtained from the adhesive rubber composition according to the present invention described above.

  The adhesive rubber composition according to the present invention can be used as it is, but it can exhibit its characteristics most when used as a crosslinked product such as an adhesive crosslinked rubber.

  As a crosslinking method, the method of heating using a crosslinking agent (SiH group containing compound (B)) and a catalyst (C) is preferable. First, the adhesive rubber composition according to the present invention is prepared, for example, by the following method.

  That is, the rubber composition for bonding according to the present invention is obtained by using an internal mixer (sealed mixer) such as a Banbury mixer, a kneader, or an intermix, with an ethylene / α-olefin / non-conjugated polyene random copolymer rubber ( A), after kneading additives such as rubber reinforcing agent, inorganic filler, softener, preferably at a temperature of 80 to 170 ° C. for 1 to 10 minutes, using rolls such as an open roll, or a kneader, SiH group-containing compound (B), catalyst (C), reaction inhibitor (D), and defoaming material are additionally mixed as necessary, kneaded at a roll temperature of 100 ° C. or lower for 1 to 30 minutes, and then dispensed. Can be prepared.

  Further, when the kneading temperature in the internal mixer is low, ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A), SiH group-containing compound (B), reaction inhibitor (D) rubber reinforcement An anti-aging agent, a colorant, a dispersant, a flame retardant, a defoaming agent and the like may be simultaneously kneaded together with an agent, an inorganic filler, a softening agent and the like.

  The adhesive rubber composition according to the present invention prepared as described above is molded into an intended shape by various molding methods using a press, an injection molding machine, a transfer molding machine, etc. The product can be introduced into a crosslinking tank and crosslinked. Among these, a press molding machine, an injection molding machine, and a transfer molding machine are suitable for cross-linking adhesion to the rubber to be bonded. A crosslinked product can be obtained by heating at a temperature of 100 to 270 ° C. for 10 seconds to 30 minutes or by irradiating light, γ-rays or electron beams by the method described above. Moreover, it can also bridge | crosslink at normal temperature.

  As an aspect of using the adhesive rubber composition of the present invention, the adhesive rubber composition of the present invention is brought into contact with the crosslinked rubber molded body that is an adherend and crosslinked by a method other than sulfur vulcanization, An embodiment in which the adhesive rubber composition is crosslinked is exemplified. In the obtained molded body, the adhesive rubber composition is bonded to the crosslinked rubber molded body. Examples include, but are not limited to, insert (injection, transfer) molding in which a cross-linked rubber of an adherend is placed in a mold and the adhesive rubber composition of the present invention is further introduced into the mold. is not.

  In the present invention, the crosslinked rubber that is the adherend of the adhesive rubber is preferably a crosslinked rubber that has been crosslinked by a method other than sulfur vulcanization. The rubber used for the crosslinked rubber is not particularly limited, but rubber made of hydrocarbon, such as ethylene / α-olefin / nonconjugated polyene copolymer, aromatic vinyl / conjugated diene copolymer or hydrogenated product thereof, Examples include butyl rubber containing isobutylene, conjugated diene polymer, and the like. Among these, ethylene / α-olefin / non-conjugated polyene copolymer rubber is preferable.

  In crosslinking these rubbers, it is preferable not to use sulfur as a vulcanizing agent. Examples of cross-linking methods other than sulfur vulcanization include cross-linking with compounds having two or more SiH groups in the molecule, cross-linking with organic peroxides, resin cross-linking, and the like, such as electron beam cross-linking without using a cross-linking agent. It may be. The crosslinked rubber also includes a thermoplastic elastomer obtained by dynamic crosslinking.

The adhesive rubber composition of the present invention has low adhesiveness with a sulfur vulcanized crosslinked rubber and often hardly adheres. Preferably, the adhesive strength with the sulfur vulcanized rubber measured by the method described later is 0.5 MPa or less.
On the other hand, the adhesive rubber of the present invention strongly adheres to a crosslinked rubber obtained by a method other than sulfur vulcanization. Therefore, it is possible to obtain a molded body having an adhesive strength equivalent to, and preferably higher than, a conventional molded body obtained from an adherend and an adhesive rubber.
In addition, when manufacturing products for which it is not appropriate to use sulfur-vulcanized crosslinked rubber, the crosslinked rubber to be adhered can be obtained by a method other than sulfur-vulcanized crosslinked rubber and sulfur vulcanization in the production process. Even if it is no longer possible to determine whether the rubber is a cross-linked rubber, it will selectively adhere to rubber obtained by a method other than sulfur vulcanization, so that the cross-linked rubber that has been accidentally sulfur vulcanized will become a product. It can be prevented from being shipped.

  Further, the bonding rubber of the present invention has high productivity because the time required for bonding is short, and also has less blooming such as a vulcanizing agent and a crosslinking aid from the bonding member as described above.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples at all.

In addition, the composition, iodine value, intrinsic viscosity [η], molecular weight distribution (Mw / Mn), and branching index of the copolymer rubber used in Examples and Comparative Examples were determined by measurement or calculation in the following manner. .
(1) Composition of copolymer rubber The composition of the copolymer rubber was measured by ¹³ C-NMR method.
(2) Iodine value of copolymer rubber The iodine value of copolymer rubber was determined by a titration method.
(3) Intrinsic viscosity [η]
The intrinsic viscosity [η] of the copolymer rubber was measured in 135 ° C decalin.
(4) Molecular weight distribution (Mw / Mn)
The molecular weight distribution of the copolymer rubber was represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC. For GPC, Tosoh Co., Ltd. GMH-HT and GMH-HTL were used for the column, and orthodichlorobenzene was used for the solvent.
(5) Branch index The frequency dispersion of the complex viscosity η ^* was measured for EPR (4 samples having different molecular weights) having no long chain branching using a dynamic viscoelasticity tester.

The complex viscosity η ^* at 0.01 rad / sec and 8 rad / sec is obtained, and the complex viscosity η _1L ^* (0.01 rad / sec) is plotted on the vertical axis, and the complex viscosity η _2L ^* (8 rad / sec) is calculated. Plotting on the horizontal axis, creating a reference line, and measuring η _1L0 ^* when η _2L ^* = 1 × 10 ³ / Pa · s on the extension of the line.

Next, similarly for the target sample, the complex viscosity η ^* at 0.01 rad / sec and 8 rad / sec is obtained, and the complex viscosity η _1B ^* (0.01 rad / sec) is plotted on the vertical axis. The rate η _2B ^* (8 rad / sec) is plotted on the horizontal axis. This plot has a larger value than the reference line, and the longer the long chain branch, the larger the distance from the reference line.

Next, the reference line was translated so as to pass over this plot, and the intersection point η _1B0 ^* with the complex viscosity η ₂ ^* = 1 × 10 ³ / Pa · s was measured. The branching index was calculated by applying the values of η _1L0 ^* and η _1B0 ^* measured as described above to the following equation.
Branch index = ( _{logη 1L0} ^* −logη _1B0 ^* ) × 10

The measurement conditions are as follows.
Reference samples: 4 types of EPR, manufactured by Mitsui Chemicals, Tafmer (registered trademark) P-0280, P-0480, P-0680, P-0880 (trade name)
-Dynamic viscoelasticity tester (RDS): Rheometrics-Sample: Used by punching a 2mm sheet into a circle with a diameter of 25mm.
・ Temperature: 190 ° C
・ Distortion rate: 1%
-Frequency dependence: 0.001-500 rad / sec

[Production Example 1]
[Production of ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (1)]
Using a stainless steel polymerization vessel (stirring rotation speed = 250 rpm) with a substantial internal volume of 100 liters equipped with stirring blades, polymerization of ethylene, propylene and 5-vinyl-2-norbornene was continuously performed at a polymerization pressure of 0.68 MPa. Original copolymerization was performed. From the side of the polymerization vessel to the liquid phase, 60 liters of hexane per hour, 3.0 kg of ethylene, 8.5 kg of propylene, 150 g of 5-vinyl-2-norbornene, 50 liters of hydrogen, VOCl ₃ as a catalyst Was continuously fed at a rate of 35 mmol, Al (Et) ₂ Cl at 163 mmol, and Al (Et) _1.5 Cl _1.5 at a rate of 47 mmol.

  When the copolymerization reaction was performed under the conditions described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber was obtained in a uniform 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 then the polymer is separated from the solvent by a steam stripping treatment, followed by vacuum at 55 ° C. for 48 hours. Drying was performed.

  Table 1 shows the physical properties of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (hereinafter sometimes referred to as copolymer 1) obtained as described above.

[Production Examples 2 to 5]
In Production Example 2, ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber having different properties was obtained by changing the polymerization conditions as in Table 1 in Production Example 1 (hereinafter referred to as Copolymer 2). Sometimes). The physical properties of the obtained copolymer 2 are shown in Table 1.

  Production Example 3 is a homogeneous solution of ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-3) having different properties by changing the polymerization conditions as shown in Table 1 in Production Example 1. Got in the 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 Diana Process Oil PW-380 (manufactured by Idemitsu Kosan Co., Ltd.) is used as (A-3) 100. After adding the polymer to 20 parts by weight and then separating the polymer from the solvent by a steam stripping treatment, vacuum drying is performed at 55 ° C. for 48 hours. From (A-3) and the oil Copolymer 3 was obtained. Table 1 shows the physical properties of the obtained (A-3).

  In Production Example 4, ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber having different properties was obtained by changing the polymerization conditions in Production Example 1 as shown in Table 1 (hereinafter referred to as Copolymer 4). Sometimes). The physical properties of the obtained copolymer 4 are shown in Table 1.

  In Production Example 5, the ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (5) having different properties was obtained by changing the polymerization conditions in Production Example 1 as shown in Table 1 (hereinafter, the same shall apply). Sometimes referred to as polymer 5). The physical properties of the obtained copolymer 5 are shown in Table 1.

[Example 1]
First, 100 parts by weight of ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (Copolymer 1) shown in Table 1, carbon black [manufactured by Asahi Carbon Co., Ltd., trade name: Asahi # 50] 85 parts by weight, 20 parts by weight of a softening agent (trade name, Diana Process Oil TMPW-380, manufactured by Idemitsu Kosan Co., Ltd.) was kneaded with a Banbury mixer (manufactured by Kobe Steel, Ltd.) having a capacity of 1.7 liters.

  As a kneading method, first, ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (copolymer 1) was kneaded for 30 seconds, and then carbon black and a softening agent were added and kneaded for 2 minutes. . Thereafter, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain a rubber compound (I-1). This kneading was performed at a filling rate of 70%.

  Next, 205 parts by weight of this compound (I-1) was added to an 8-inch roll (front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm. ), 3 parts by weight of a SiH group-containing compound (* 1) represented by the following formula [III], 0.3 parts by weight of 1-ethynyl-1-cyclohexanol [manufactured by BASF] as a reaction control agent, oxidation After adding 4 parts by weight of calcium [manufactured by Inoue Lime Industry Co., Ltd., Vesta PP] and kneading for 10 minutes, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetra is used as a catalyst. After adding 0.2 part by weight of a siloxane-platinum complex [manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-93-1410] and kneading for 5 minutes, the kneaded product was dispensed into a sheet (II-1). The separated sheet (II-1) was pressed at 180 ° C. for 2 minutes using a 150-ton press molding machine to prepare a crosslinked rubber sheet (A) having a thickness of 2 mm.

(* 1)
(However, in the compound represented by the formula [III], (—Si (CH ₃ ) ₂ O—), (—Si (H) CH ₃ —O—), (—SiPh) _(2- O-) each structural unit is bonded at random, and Ph represents a phenyl group.)
In addition, according to JIS K6300 (1994), “tc (90)” is used as a measure of the crosslinking rate of the above-mentioned dispensing sheet before thermosetting, using JSR Clastometer Type 3 (manufactured by Nippon Synthetic Rubber Co., Ltd.). The measurement was performed at 180 ° C. The difference between the minimum value ML and the maximum value MH of torque obtained from the crosslinking (vulcanization) curve was defined as ME (= MH-ML), and the time to reach 90% ME was defined as tc (90).
Further, according to JIS K6300 (1994), the scorch time t5 was measured at 125 ° C.

(6) Evaluation of roll processability The roll processability of the material (rubber composition) was determined by the following three-step evaluation.
A: Can be processed without problems as a general millable rubber (Standard: Can be kneaded in a predetermined time in accordance with the kneading method B1 of JIS K6395 (1997))
B: Difficult to process as a general millable rubber (standard: one that takes 1 to 2 times the predetermined time according to the kneading method B1 of JIS K6395 (1997))
C: A rubber that cannot be processed at all as a general millable rubber (Standard: A thing that takes more than twice the predetermined time according to the kneading method B1 of JIS K6395 (1997))

(7) Evaluation of injection moldability About the above-mentioned dispensing sheet before thermosetting, injection molding was performed under the following conditions using a 75-ton injection molding machine: model VI75P-40 / 60SPR5P (500) manufactured by Matsuda Seisakusho. The material was handled and the length (hereinafter referred to as flow length) flowing through the mold was measured.
Flow length Injection molding was performed under the following conditions, and the flow length flowing in a mold having a width of 7 mm and a depth of 1 mm was measured. The better the flowability, the longer the flow length.
Driving amount = 10 g Injection temperature = 180 ° C. Screw diameter = 40 mm
Clamping pressure = 75 tons Injection pressure = 180 MPa Injection time = 12 seconds Crosslinking time = 90 seconds

(8) Evaluation of adhesiveness About the above-mentioned dispensing sheet before thermosetting, 75-ton injection molding machine manufactured by Matsuda Seisakusho: Model VI75P-40 / 60SPR5P (500) is used for injection molding under the following conditions. The adhesive strength was measured by performing cross-linking adhesion with two kinds of adherend rubbers.

  When the adhesive strength is measured under the following test conditions, a case where the adhesive strength is 0.5 MPa or less is defined as not bonding.

[When the adherend rubber is sulfur vulcanized rubber]
Trade name as rubber: 130 parts by weight of Mitsui Eptalloy (registered trademark) PX-049PE, carbon black [manufactured by Asahi Carbon Co., Ltd., trade name: Asahi # 60G], calcium carbonate [Shiraishi Calcium Co., Ltd. ), Trade name Whiten SB] 30 parts by weight, softener [Idemitsu Kosan Co., Ltd., trade name Diana Process Oil TMPW-380] 80 parts by weight, zinc white 5 parts by weight, stearic acid 1 part by volume The mixture was kneaded with a 7 liter Banbury mixer [manufactured by Kobe Steel, Ltd.].

  As a kneading method, PX-049PE was first kneaded for 30 seconds, and then carbon black, calcium carbonate, zinc white, stearic acid, and a softening agent were added and kneaded for 2 minutes. Thereafter, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain a rubber compound (I-1). This kneading was performed at a filling rate of 70%.

Next, 406 parts by weight of this formulation is wound on an 8-inch roll (front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), 0.8 part by weight of sulfur, 0.8 part by weight of accelerator MBT (manufactured by Sanshin Chemical Industry Co., Ltd., Suncera-M), 1.0 part by weight of accelerator TMTD (manufactured by Sanshin Chemical Industry Co., Ltd., Suncera-TT) , Accelerator ZnBDC (Sansera-BZ, manufactured by Sanshin Chemical Industry Co., Ltd.) 2.0 parts by weight, Accelerator CBS (Sansera-CM, manufactured by Sanshin Chemical Industries Co., Ltd.) 1.0 part by weight, Accelerator (Sanshin After adding 1.0 part by weight of Chemical Industrial Co., Ltd. (Sanfel R) and kneading for 10 minutes, the kneaded material was taken out into a sheet and pressurized at 180 ° C. for 10 minutes using a 150-ton press machine, thickness 2 mm Prepared crosslinked rubber sheet It was. This crosslinked rubber sheet was punched into a JIS No. 3 dumbbell shape. This dumbbell shape is cut in half at the center of the vote line, the half is set in an injection mold, and the rubber composition for the adhesive rubber is injection molded under the following conditions to the other half of the dumbbell. A part was formed and cross-linked. After the injection molding, the dumbbell-shaped rubber was taken out and subjected to a tensile test according to JIS K6251 (1993), and the tensile strength at break was defined as the adhesive strength.
Injection molding conditions:
Driving amount = 1 g Injection temperature = 180 ° C. Screw diameter = 40 mm
Clamping pressure = 75 tons Injection pressure = 180 MPa Injection time = 12 seconds Crosslinking time = 90 seconds

[When the adherend rubber is a rubber cross-linked with a SiH group-containing compound]
First, 120 parts by weight of ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (Copolymer 3) shown in Table 1, carbon black [Asahi Carbon Co., Ltd., trade name: Asahi # 50] 160 parts by weight, calcium carbonate [manufactured by Shiraishi Calcium Co., Ltd., trade name Whiten SB] 30 parts by weight, polyethylene [manufactured by Mitsui Chemicals, Inc., trade name ULTZEX 2022F], softener [Idemitsu Kosan] 70 parts by weight of Diana Process Oil TMPW-380, manufactured by Co., Ltd., and trade name were kneaded with a Banbury mixer [manufactured by Kobe Steel, Ltd.] having a capacity of 1.7 liters.

  As a kneading method, first, ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (copolymer 3) was kneaded for 30 seconds, and then carbon black and a softening agent were added and kneaded for 2 minutes. . Thereafter, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 150 ° C. to obtain a rubber compound (I-1). This kneading was performed at a filling rate of 70%.

  Next, 400 parts by weight of this compound (I-1) was added to an 8-inch roll (front roll surface temperature 50 ° C., rear roll surface temperature 50 ° C., front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm. 4 parts by weight of a SiH group-containing compound * 1 represented by the following formula [III] and 0.3 part by weight of 1-ethynyl-1-cyclohexanol [manufactured by BASF] as a reaction control agent is added for 10 minutes. After kneading, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane-platinum complex [manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-93-1410 as a catalyst After adding 0.4 part by weight and kneading for 5 minutes, the kneaded product was separated into sheets (II-1). The separated sheet (II-1) was pressed at 180 ° C. for 2 minutes using a 150-ton press molding machine to prepare a crosslinked rubber sheet (A) having a thickness of 2 mm. This crosslinked rubber sheet was punched into a JIS No. 3 dumbbell shape. This dumbbell shape is cut in half at the center of the vote line, and the half is set in an injection mold. The rubber composition for the adhesive rubber is injected into the remaining half by injection molding under the following conditions. Molded and cross-linked. After the injection molding, the dumbbell-shaped rubber was taken out and subjected to a tensile test according to JIS K6251 (1993), and the tensile strength at break was defined as the adhesive strength.

Injection molding conditions:
Driving amount = 1 g Injection temperature = 180 ° C. Screw diameter = 40 mm
Clamping pressure = 75 tons Injection pressure = 180 MPa Injection time = 12 seconds Crosslinking time = 90 seconds
The following measurement was performed using the obtained crosslinked rubber sheet (A) having a thickness of 2 mm.

(9) Strength characteristics A tensile test was performed according to JIS K6251 (1993) to determine the tensile breaking strength and the tensile breaking elongation.

(10) Compression set According to JIS K6262 (1997), compression set was measured under the condition of 150 ° C. × 22H.

(11) Heat aging resistance According to JIS K6257 (1993), a tensile test was conducted after heat aging under the conditions of 150 ° C. × 70 H, and the retention rate of tensile strength at break was measured.

(12) Odor resistance Qualitative evaluation of odor was performed by the following three-stage evaluation by 20 people who randomly selected the obtained crosslinked rubber sheet having a thickness of 2 mm.
A: 15 or more people judged to be odorless B: 5 to 14 people judged to be odorless C: 5 or more people judged to be odorous

(13) Sheet Metal Contamination Contamination test was performed according to JIS K6267 (1996). As a material to be contaminated, steel F25C was used. The test was conducted under the following conditions using a xenon arc lamp type weather resistance tester. After the test, the degree of contamination was evaluated in the following three stages.
Thermostatic bath temperature = 70 ° C. Irradiation time = 24 hours Irradiation method = continuous Surface temperature = 55 ° C. at black panel temperature
Irradiance on surface of contaminated material = 550 w / m ² at wavelength of 300 to 800 nm
A: Sheet metal is not contaminated B: Sheet metal is slightly contaminated C: Sheet metal is contaminated
These results are shown in Table 3.

[Examples 2 to 5, Comparative Example 1]
The experiment was conducted in the same manner as in Example 1 according to the formulation shown in Table 2.
The results are shown in Table 3.

[Comparative Example 2]
The experiment was conducted in the same manner as in Example 1 according to the formulation shown in Table 2.
That is, instead of copolymer 1, 100 parts by weight of copolymer 6 (trade name: Mitsui EPT4010, manufactured by Mitsui Chemicals), 1 part by weight of polyethylene glycol (trade name: PEG # 4000, manufactured by Lion Corporation), Instead of using 5 parts by weight of zinc white and 1 part by weight of stearic acid, and using three compounds of SiH group-containing compound, siloxane complex-2% platinum catalyst and 1-ethynyl-1-cyclohexanol, the accelerator MBT ( Sanshin Chemical Industry Co., Ltd., trade name Suncera-M) 0.5 part by weight accelerator, ZnBDC (Sanshin Chemical Industry Co., Ltd., trade name Suncera-BZ) 0.3 part by weight, sulfur 0.8 weight The composition was the same as in Example 1 except for using a part. The test was performed in the same manner as in Example 1. The results are shown in Table 3.
Examples 1-5 show that the crosslinked rubber obtained by sulfur vulcanization does not adhere, but adheres well to the crosslinked rubber obtained by methods other than sulfur vulcanization. In particular, Example 1-3 has high adhesive strength. Comparative Example 1 is not a millable type because the viscosity is too low, and the general-purpose injection molding machine has poor workability and also has low strength characteristics when crosslinked. Comparative Example 2 is a conventional sulfur vulcanizing type adhesive rubber, but it is not only poor in sealing properties, (compression set) and heat aging resistance, but also adheres to sulfur vulcanized rubber, so it is selectively bonded. Cannot be achieved.

  The composition for an adhesive rubber of the present invention is suitable for adhesion to a crosslinked rubber obtained by a method other than sulfur vulcanization, and has rubber elasticity, flexibility, weather resistance, water resistance, heat aging resistance, cold resistance, Vulcanized rubber because it is an adhesive rubber composition with excellent sealability, adhesiveness, environmental safety and hygiene, odor resistance, and bloom resistance, as well as excellent fluidity during molding and a short molding cycle. They can be bonded to each other, and can be suitably used, for example, for parts made of a plurality of vulcanized rubbers, weather strips for automobiles, and the like.

Claims (4)

Ethylene / α-olefin / nonconjugated polyene random copolymer rubber (A) having a structural unit derived from at least one nonconjugated polyene represented by the following general formula [I] or [II], and one molecule of SiH group A millable type comprising an SiH group-containing compound (B) having at least two therein and a catalyst (C), and for bonding with a crosslinked rubber obtained by a method other than sulfur vulcanization. Rubber composition for bonding;

[Wherein 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] ,

[Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]. Ethylene / α-olefin / nonconjugated polyene random copolymer rubber (A) having a structural unit derived from at least one nonconjugated polyene represented by the following general formula [I] or [II], and one molecule of SiH group It consists of a SiH group-containing compound (B) having at least two, a catalyst (C), and a reaction inhibitor (D), and is for adhesion to a crosslinked rubber obtained by a method other than sulfur vulcanization. A millable adhesive rubber composition characterized by the above;

[Wherein 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] ,

[Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms]. The rubber composition for bonding according to claim 1, wherein the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) has the following characteristics.
(I) The molar ratio of ethylene to the α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin) is in the range of 60/40 to 90/10, and (ii) the iodine value is in the range of 1 to 30. (Iii) The intrinsic viscosity [η] measured with a decalin solution at 135 ° C. is in the range of 0.95 to 4 dl / g, and (iv) the branching index is in the range of 3 to 20. An adhesive member obtained from the adhesive rubber composition according to any one of claims 1 to 3.