JP2005298593A - Adhered rubber sealing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sealing material excellent in resistance to blooming, resistance to environmental deterioration, resistance to sealing, and resistance to offensive smell, and further excellent in adhesive force. <P>SOLUTION: This sealing material is formed by adhering a crosslinked material comprising (P) a rubber composition to (Q) a crosslinked rubber or to (R) a thermoplastic elastomer (R), wherein the rubber composition (P) contains (A) an ethylene-α-olefin-nonconjugated polyene random copolymer rubber having structural units derived from at least one kind of nonconjugated polyene of norbornene compound, (B) an SiH radical-containing compound having at least two SiH radicals in its molecule, and (C) a catalyst, and the crosslinked rubber (Q) is crosslinked by a procedure other than sulfur vulcanization. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an adhesive rubber seal material. More specifically, the adhesive portion is not peeled off, and rubber elasticity, flexibility, weather resistance, water resistance, heat aging resistance, cold resistance, seal resistance, and adhesiveness are disclosed. The present invention relates to a bonded rubber seal material that is excellent in environmental safety and hygiene, odor resistance, and bloom resistance, and that can shorten a molding cycle.

The manufacturing method for automobile weather strips, etc., is a method of continuously extrusion-crosslinking EPDM with a rubber composition comprising a reinforcing material such as carbon black or white filler, a plasticizer, sulfur, a vulcanization accelerator, and the like. The straight part is manufactured. Next, a rubber composition (injection material) having excellent fluidity, which is made of EPDM with a reinforcing material such as carbon black or white filler, a plasticizer, sulfur, a vulcanization accelerator and the like, is produced. And it manufactures by inject | pouring the rubber composition which is excellent in fluidity | liquidity between bridge | crosslinked linear parts, and carrying out vulcanization adhesion. However, the weather strip material for automobiles manufactured in this way has a long vulcanization adhesion time and a high production cost, and recently, a plastic elastomer has been used as an injection material. (See, for example, Technical Document 1)
JP 2003-003023 A

  Although this method shortens the bonding time, the cross-linked straight portion has improved appearance and environmental degradation resistance (weather resistance, heat aging resistance) due to blooming of the vulcanizing agent and vulcanization accelerator. May be inferior. 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 to people in the vehicle. However, the sealing performance and odor resistance may be inferior.

  Therefore, it is difficult for the adhesive part to peel off, and it is excellent in bloom resistance, environmental degradation resistance (weather resistance, heat aging resistance), seal resistance, and odor resistance, and can shorten the cross-linking adhesion time. A seal material that can maintain the flexibility, water resistance, and cold resistance of EPDM is desired.

  The problem to be solved is to provide a sealing material that is excellent in bloom resistance, environmental degradation resistance, seal resistance, odor resistance, and excellent adhesive strength.

  The sealing material of the present invention is an 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 a crosslinked product obtained from a SiH group-containing compound (B) having at least two SiH groups in one molecule, a rubber composition (P) containing a catalyst (C), and a method other than sulfur vulcanization. The crosslinked rubber (Q) or the thermoplastic elastomer (R) is bonded.

[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 sealing material of the present invention is an 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 a crosslinked product obtained from a SiH group-containing compound (B) having at least two SiH groups in one molecule, a rubber composition (P) containing a catalyst (C), and a method other than sulfur vulcanization. The crosslinked rubber (Q) or the thermoplastic elastomer (R) is bonded, and the bonded portion is difficult to peel off. Weather resistance, heat aging resistance), environmental degradation resistance, seal resistance, odor resistance, cross-linking adhesion time can be shortened, and the flexibility, water resistance, Can maintain cold resistance Sheet - it is possible to obtain a sealing material.

  Hereinafter, the sealing material of the present invention will be described in detail.

  The rubber composition (P) used in the production of the sealing material of the present invention comprises an ethylene / α-olefin / having a structural unit derived from at least one non-conjugated polyene represented by the general formula [I] or [II]. Non-conjugated polyene random copolymer rubber (A), SiH group-containing compound (B) having at least two SiH groups in one molecule, and catalyst (C) are included.

[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 such α-olefins 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 may be used alone or in combination of two or more.

  The non-conjugated polyene used in the present invention is a 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-hexyl) -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 seal material excellent in rubber elasticity, flexibility, weather resistance, heat aging resistance, seal resistance, strength characteristics, and cold resistance 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 seal material excellent in rubber elasticity, flexibility, weather resistance, heat aging resistance, and seal resistance can be obtained.

(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 1.8 to 5 dl / g, more preferably It is desirable to be 2.5 to 4 dl / g, particularly preferably 3.0 to 4 dl / g, and most preferably 3.2 to 3.8.
When the intrinsic viscosity [η] is within the above range, a seal material excellent in rubber elasticity and strength characteristics 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 5 to 30, more preferably 7 to 25, Preferably it is 10-20. If the value of this branching index is 5 or more, the surface skin is good when the linear part is formed by extrusion, and if it is 20 or less, the elongation property at the time of tensile fracture is excellent and the adhesive strength is sufficient. .

(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. When the molecular weight distribution is 2 or more, the extrudability is improved. On the other hand, a molecular weight distribution of 200 or less is preferable in terms of 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.

As such a SiH group-containing compound (B), a compound represented by the following general composition formula R ⁴ _b H _c SiO _{(4-bc) / 2} can be usually 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 in the formula 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 0.1 to 100 parts by weight, preferably 0.1 to 75 parts by weight, per 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). More preferably 0.1 to 50 parts by weight, still more preferably 0.2 to 30 parts by weight, still more preferably 0.2 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, most preferably 0. Used in a proportion of 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, and the crosslinking density is moderate and the strength characteristics and elongation are high. A seal rubber having excellent characteristics can be obtained. If the SiH group-containing compound (B) is used in a proportion exceeding 100 parts by weight, it may be disadvantageous 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 seal material having a moderate crosslinking density and excellent strength properties and elongation properties can be obtained, and a front portion excellent in crosslinking rate can be produced. 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, a rubber composition for producing a linear part 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 composition for producing the linear portion of the present invention comprises the component (A), the component (B) and the component (C) as described above, and the component (D) may be present if necessary. Good. Further, in the rubber composition according to the present invention, a conventionally known rubber reinforcing agent, inorganic filler, softening agent, anti-aging agent, processing aid, vulcanization accelerator, organic, depending on the intended use of the cross-linked product. Additives such as 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.

  The crosslinkable rubber composition 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 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 a crosslinked rubber for adhesion.

  As a crosslinking method, either a heating method using a crosslinking agent (SiH group-containing compound (B)) and a catalyst (C), or a method using light, γ-ray, or electron beam irradiation may be employed. First, the adhesive rubber composition according to the present invention is prepared, for example, by the following method.

  That is, the rubber composition according to the present invention is produced by using an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) by an internal mixer (sealed mixer) such as a Banbury mixer, a kneader, or an intermix. After kneading additives such as a rubber reinforcing agent, an inorganic filler, and a softener, preferably at a temperature of 80 to 170 ° C. for 1 to 10 minutes, a roll such as an open roll or a kneader is used to form a SiH group. Prepared by adding the compound (B), catalyst (C), reaction inhibitor (D), and defoamer as necessary, kneading at a roll temperature of 100 ° C. or lower for 1 to 30 minutes, and dispensing. can do.

  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 rubber composition (P) prepared according to the present invention and used for a straight portion such as a weather strip, for example, is as follows.
It is molded into the desired shape by various molding methods using an extrusion molding machine, calendar roll, press, injection molding machine, transfer molding machine, etc., and the molded product is introduced into the vulcanizing tank at the same time as molding or is crosslinked. Can do. Of these, an extruder is suitable for obtaining the straight portion. A crosslinked product is obtained by heating at a temperature of 100 to 270 ° C. for 1 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.

  In this crosslinking step, a mold may be used, or the crosslinking may be performed without using a mold. When a mold is not used, the molding and crosslinking processes are usually carried out continuously. As a heating method in the vulcanization tank, a heating tank such as hot air, glass bead fluidized bed, UHF (ultra-high frequency electromagnetic wave), steam or the like can be used.

[Crosslinked rubber (Q)]
Next, a crosslinkable rubber composition that is a raw material for the crosslinked rubber (Q) will be described.

  The crosslinked rubber (Q) of the present invention is a crosslinked rubber 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.

  Particularly suitable as these crosslinkable rubber compositions are ethylene / α-olefin / nonconjugated polyenes having structural units derived from at least one nonconjugated polyene represented by the above general formula [I] or [II]. Examples include a composition comprising a random copolymer rubber (AA) and a crosslinking agent (BB) other than sulfur. In particular, one molecule of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (AA) and SiH group. A crosslinkable rubber composition containing at least two SiH group-containing compounds (BB1) and a catalyst (CC) is desirable.

[Ethylene / α-olefin / non-conjugated polyene random copolymer rubber (AA)]
Examples of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (AA) suitably used in the present invention include those used in the composition (P). (I) Molar ratio of ethylene and α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin), (v) polyene content, (ii) iodine value, and (vi) molecular weight distribution, the composition (P ) Is the same as that used in).

(Iii) Intrinsic viscosity The intrinsic viscosity [η] of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (AA) 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 a rubber for injection excellent in rubber elasticity and strength properties can be obtained, and also excellent in adhesiveness and roll processability, press molding, injection A rubber composition for injection excellent in fluidity during molding and transfer molding can be obtained.
(Iv) Branching index The branching index determined from a dynamic viscoelasticity measuring device of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (AA) is preferably 3 to 20, more preferably 5 to 20, Preferably it is 7-20. When the branching index value is 3 or more, the viscosity in the low shear rate region is not low, and the rubber composition for injection is not sticky. Therefore, the handling properties during press molding, injection molding, and transfer molding are good. . Moreover, the elongation characteristic at the time of a tensile fracture is favorable in it being 20 or less, and adhesive strength is high.

Cross-linking agents other than sulfur (BB)
The crosslinking agent (BB) other than sulfur used in the present invention reacts with, for example, ethylene / α-olefin / non-conjugated polyene random copolymer rubber (AA) to act as a crosslinking agent. Here, sulfur in the case of a crosslinking agent other than sulfur is sulfur used for so-called ordinary rubber vulcanization. Therefore, even if a sulfur atom happens to be present when the cross-linking agent is represented by a structural formula, the case where the sulfur atom itself does not participate in the cross-linking does not correspond to the sulfur in the case of a cross-linking agent other than sulfur. The crosslinking agent used in the production of the (Q) crosslinked rubber of the present invention preferably comprises only a crosslinking agent other than sulfur.

  Specific examples of the crosslinking agent (BB) other than sulfur include an organic peroxide (BB2) that is crosslinked by a radical reaction, and a SiH group-containing compound (BB1) that is crosslinked by a hydrosilylation reaction.

Specific examples of the organic peroxide (BB2) include dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butyl cumylper. Oxide, di-t-amyl peroxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3, 2,5-dimethyl-2,5-di Dialkyl peroxides such as (benzoylperoxy) hexane, 2,5-dimethyl-2,5-mono (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene Kind;
t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxymaleic acid, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, di -Peroxyesters such as t-butyl peroxyphthalate;
Ketone peroxides such as dicyclohexanone peroxide;
And a mixture thereof. Among them, organic peroxides having a half-life of 1 minute in the range of 130 to 200 ° C. are preferable, and in particular, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3. , 5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, t-butyl hydroperoxide and other organic peroxides are preferred.

  Moreover, as a compound (BB1) which contains 2 or more of SiH groups in 1 molecule, the compound similar to the (B) component used in the said composition (P) can be mentioned. When (BB1) is used, in the same manner as the component (B), 0.1 to 100 parts by weight, preferably 100 parts by weight of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (AA), 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, still more preferably 0.2 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight. Part by weight, most preferably 0.5 to 5 parts by weight is used.

  When using a compound (BB1) containing two or more SiH groups in one molecule, the catalyst (CC) and reaction inhibitor (DD) optionally used are the same as those used in the composition (P). Can be mentioned. In particular, from the viewpoint of crosslinking rate, a compound (BB1) containing two or more SiH groups in one molecule is preferable. Moreover, when using a catalyst (CC), it is 0.1-100,000 weight ppm with respect to ethylene * alpha-olefin * nonconjugated polyene random copolymer rubber (AA) like the said (C) component, Preferably Is used in a proportion of 0.1 to 10,000 ppm by weight, more preferably 1 to 5,000 ppm by weight, and particularly preferably 5 to 1,000 ppm by weight. When the reaction inhibitor (DD) is used, 0 to 50 parts by weight, usually 100 parts by weight of ethylene / α-olefin / non-conjugated polyene random copolymer rubber (AA), as in the case of the component (D). 0.0001-50 parts by weight, preferably 0.0001-30 parts by weight, more preferably 0.0001-20 parts by weight, still more preferably 0.0001-10 parts by weight, particularly preferably 0.0001-5 parts by weight It is used in the ratio.

  According to the present invention, in a crosslinkable rubber composition that is a raw material of the crosslinked rubber (Q) crosslinked by a method other than sulfur, a conventionally known rubber reinforcing agent, depending on the intended use of the crosslinked product, Additives such as inorganic fillers, softeners, anti-aging agents, processing aids, vulcanization accelerators, organic peroxides, crosslinking aids, foaming agents, foaming aids, colorants, dispersants, flame retardants, It can mix | blend in the range which does not impair the objective of this invention. These are the same as described in the rubber composition (P), and the blending ratio with respect to rubber, for example, ethylene / α-olefin / non-conjugated polyene copolymer (AA) is also ethylene / α-olefin / non-conjugated polyene. The ratio is the same as that for the copolymer (A). Among these, when a compound having two or more (BB1) SiH groups in one molecule is used as a cross-linking agent, the component to be blended preferably does not inhibit the hydrosilylation reaction of the alkene.

The crosslinkable rubber composition, which is a raw material of the crosslinked rubber (Q) crosslinked by a method other than sulfur vulcanization according to the present invention, can be used as it is uncrosslinked, but most when used as a crosslinked product. The characteristic can be exhibited.
As the crosslinking method, either a method of crosslinking by heating, for example, using a crosslinking agent other than sulfur, or a method of irradiation with light, γ rays or electron beams may be employed. First, an adhesive rubber composition according to the present invention comprises an ethylene / α-olefin / non-conjugated polyene random copolymer (AA), a compound (BB1) having two or more SiH groups in one molecule, and a catalyst (CC). For example, it is prepared by the following method.

  That is, the rubber composition according to the present invention is produced by using an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (AA) by an internal mixer (sealed mixer) such as a Banbury mixer, a kneader, or an intermix. After kneading additives such as a rubber reinforcing agent, an inorganic filler, and a softener, preferably at a temperature of 80 to 170 ° C. for 1 to 10 minutes, a roll such as an open roll or a kneader is used to form a SiH group. Prepared by adding the compound (BB1), catalyst (CC), reaction inhibitor (DD), and defoamer as necessary, kneading at a roll temperature of 100 ° C. or lower for 1 to 30 minutes, and dispensing. can do.

When the kneading temperature in the internal mixer is low, ethylene / α-olefin / non-conjugated polyene random copolymer rubber (AA), SiH group-containing compound (BB1), reaction inhibitor (DD) 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.
Moreover, the rubber composition which has another crosslinking agent can be prepared in accordance with a conventional method.

The crosslinkable rubber composition according to the present invention prepared as described above,
It is molded into the desired shape by various molding methods using a press, injection molding machine, transfer molding machine, etc., and the molded product is introduced into a crosslinking tank at the same time as molding or is crosslinked to give a crosslinked product (Q). be able to. 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.

[Thermoplastic elastomer (R)]
Although there is no restriction | limiting in particular in the thermoplastic elastomer R used by this invention, The thing as described in the following literature is preferable.

Plastic Age, Vol. 42, No. 2, (1996), Polymer Digest, Vol. 54, No. 4 (2002) (Rubber Digest Co., Ltd.), Plastics Vol 54, No. 4 3 (2003) (Japan Plastics Federation), JP2003-003023, JP2003-155386, JP2003-155387, sorry for the company number.
JP-A-2003-155386, JP-A-2003-155386, JP-A-2003-003023, JP-A-2003-253055, JP-A-2003-311886, JP-A-2003-147133, and the like are preferable.

  Examples of the thermoplastic elastomer include olefin-based thermoplastic elastomers, and are composed of a crystalline polyolefin such as polypropylene and a low crystalline polyolefin such as ethylene / α-olefin / non-conjugated polyene copolymer as required. A plastic elastomer is preferably mentioned. The low crystalline polyolefin may be partially or fully cross-linked, for example.

[Seal production method]
As the method for producing the sealing material of the present invention, specifically, the crosslinkable rubber composition of the present invention is brought into contact with the crosslinked rubber (P) obtained from the rubber composition as an adherend, and then bonded. The aspect which makes the rubber composition for bridge | crosslinking adhere | attach a crosslinked rubber (P) and crosslinked rubber (Q) is mentioned. In the obtained molded body, the adhesive rubber composition is bonded to the crosslinked rubber molded body. Examples thereof include, but are not limited to, insert molding in which a cross-linked rubber of an adherend is disposed in a mold and the adhesive rubber composition of the present invention is further introduced into the mold.

In the present invention, the thermoplastic elastomer (R) may be bonded to the crosslinked rubber (P) obtained from the rubber composition as the adherend. In this case as well, insert molding or the like in which a crosslinked rubber of an adherend similar to the above is placed in a mold and the adhesive rubber composition of the present invention is further introduced into the mold may be mentioned. is not.
As these insert molding methods, conventionally known methods can be used.

  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 13C-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 (copolymer 1)]
Using a stainless steel polymerization vessel (stirring rotation speed = 250 rpm) having a substantial internal volume of 100 liters equipped with a stirring blade, a polymerization pressure of 0.74 MPa and continuously three of ethylene, propylene and 5-vinyl-2-norbornene. Original copolymerization was performed. From the side of the polymerization vessel to the liquid phase, 60 liters of hexane per hour, 3.7 kg of ethylene, 12 kg of propylene, 240 g of 5-vinyl-2-norbornene, 20 liters of hydrogen, 22 VOCl ₃ as a catalyst Mmol, Al (Et) ₂ Cl at 66 mmol, and Al (Et) _1.5 Cl _1.5 at a rate of 66 mmol continuously.

  When the copolymerization reaction was performed under the conditions described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer was obtained in a uniform solution state. The physical properties are shown in Table 1 as the physical properties of Copolymer 1.

  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-1) 100. After adding 20 parts by weight with respect to parts by weight, the polymer was separated from the solvent by a steam stripping treatment, and then vacuum-dried at 55 ° C. for 48 hours.

  As described above, an oil-extended rubber, ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (hereinafter referred to as copolymer 1) was obtained.

[Production Example 2]
[Production of ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (copolymer 2)]
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 carried out under the conditions as described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer was obtained in a uniform solution state. The physical properties of the copolymer 2 are shown in Table 1.

  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.

  As described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (hereinafter referred to as copolymer 2) was obtained.

[Example 1]
First, 120 parts by weight of ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (copolymer 1) shown in Table 1, polyethylene [Mitsui Chemicals, Ultzex (registered trademark) 2022F] 20 weight Parts, carbon black [Asahi Carbon Co., Ltd., trade name Asahi # 60G] 165 parts by weight, calcium carbonate [Shiraishi Calcium Co., Ltd., trade name Whiten SB] 30 parts by weight, softener [Idemitsu 60 parts by weight of Kosan Co., Ltd., trade name Diana Process Oil TMPW-380] was kneaded with a 1.7 liter Banbury mixer (manufactured by Kobe Steel).

  The kneading method involves first kneading ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (copolymer 1) and polyethylene for 30 seconds, and then adding carbon black, calcium carbonate and softener. Kneaded for 2 minutes. Thereafter, the ram was raised and cleaned, and further kneaded for 1 minute and discharged at about 160 ° C. to obtain a rubber compound (P-1). This kneading was performed at a filling rate of 70%.

  Next, 395 parts by weight of this compound (P-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. ), 3.5 parts by weight of the SiH group-containing compound (* 1) represented by the following formula [III], and 0.3 parts by weight of 1-ethynyl-1-cyclohexanol (manufactured by BASF) as a reaction control agent And kneading for 10 minutes, and then 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane-platinum complex [manufactured by Shin-Etsu Chemical Co., Ltd., trade name X -93-1410] After adding 0.2 parts by weight and kneading for 5 minutes, the kneaded product was dispensed into a sheet. The sheet thus obtained was extruded using a 50 mm extruder [Mitsubishi Kogyo Co., Ltd.] at an extrusion rate of 2 m / min, crosslinked at 8 ° HAV oven at 230 ° C. for 4 minutes, and 2 mm thick and wide. A straight part of 2 cm was prepared (A-1).

(However, in the compound represented by the formula [III], (—Si (CH ₃ ) ₂ O—), (—Si (H) CH ₃ —O—), (—Si (Each structural unit of (Ph) _2- O-) is bonded at random, and Ph represents a phenyl group.)
Subsequently, 100 parts by weight of ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (Copolymer 2) 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 (manufactured by Idemitsu Kosan Co., Ltd., trade name Diana Process Oil TMPW-380) was kneaded with a Banbury mixer with a capacity of 1.7 liters (manufactured by Kobe Steel). .

  As a kneading method, first, ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (Copolymer 2) 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. This kneading was performed at a filling rate of 70%.

  Next, 205 parts by weight of this compound (Q-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 the SiH group-containing compound (* 1) represented by the formula [III] described above, and 0.3 parts by weight of 1-ethynyl-1-cyclohexanol (manufactured by BASF) as a reaction control agent. In addition, after kneading for 10 minutes, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane-platinum complex [manufactured by Shin-Etsu Chemical Co., Ltd., trade name X- 93-1410] After adding 0.2 part by weight and kneading for 5 minutes, the kneaded product was dispensed into a sheet (Q-1).

  A JIS No. 3 dumbbell shape was punched from a cross-linked rubber sheet of a straight part (A-1) having a thickness of 2 mm and a width of 2 cm. Cut this dumbbell shape in half at the center of the vote line, set the half in an injection mold, and inject the rubber composition extracted into the remaining half of the mold under the following conditions. Molded and cross-linked. The time required for the cross-linking adhesion was determined as tc (90) of the sheet (Q-1), and measured at 180 ° C. according to JIS K6300 (1994). tc (90) was 0.9 minutes, and this time was determined as the time required for curing. Further, the dumbbell-shaped rubber was taken out after the injection molding, and a tensile test was conducted according to JISK6251 (1993), and the tensile strength at break was defined as the adhesive strength. The adhesive strength was 6 MPa.

Injection conditions Made by Matsuda Seisakusho, 75-ton injection molding machine: Model VI75P-40 / 60SPR5P (500)
Driving amount = 1 g Injection temperature = 180 ° C. Screw diameter = 40 mm
Clamping pressure = 75 tons Injection pressure = 180 MPa Injection time = 5 seconds

The following measurements were performed using the bonded dumbbell-shaped rubber.
(1) Compression set According to JIS K6262 (1997), the compression set was measured under the condition of 150 ° C. × 22H.
(2) Bloom resistance test The dumbbell-shaped rubber adhered in hot water (distilled water) at 70 ° C. was immersed, taken out after standing in an oven for 24 hours, and the rubber surface was observed. Whether it changed compared with the sample before immersion was observed.
(3) Sheet metal contamination test 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
As a result, the compression set was 19%, there was no change in the bloom resistance test, and the sheet metal was not contaminated even by sheet metal contamination.

[Example 2]
In the formulation (Q-1) of Example 1, 3 parts by weight of the SiH group-containing compound * 1 represented by the formula [III], 1-ethynyl-1-cyclohexanol [manufactured by BASF] 0 as a reaction control agent .3 parts by weight, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane-platinum complex [manufactured by Shin-Etsu Chemical Co., Ltd., trade name X-93-1410 ] Instead of adding 0.2 parts by weight, the same procedure as in Example 1 except that 4 parts by weight of an organic peroxide [Nippon Yushi Co., Ltd., trade name Perhexa 3M-40C] was added and kneaded for 10 minutes. This was carried out to obtain a dispensing sheet (Q-2).
tc (90) was 1.4 minutes, and this time was set as the time required to cure.

  The adhesive strength was 5.5 MPa. Further, the compression set was 20%, there was no change in the bloom resistance test, and the sheet metal was not contaminated even by sheet metal contamination.

[Example 3]
Example 1 is the same as Example 1 except that instead of the dispensing sheet (Q-1) of Example 1, a thermoplastic elastomer [Mitsui Chemical Co., Ltd., Miralaster (registered trademark) G751B] (R-3) was used. The same was done.
The time required for curing was 1 minute.

  The adhesive strength was 6 MPa. Further, the compression set was 25%, there was no change in the bloom resistance test, and the sheet metal was not contaminated even by sheet metal contamination.

[Comparative Example 1]
EPDM [manufactured by Mitsui Chemicals, Inc., trade name: Mitsui EPT3090E] 110 parts by weight, polyethylene [manufactured by Mitsui Chemicals, Ultzex (registered trademark) 2022F], 20 parts by weight, carbon black [manufactured by Asahi Carbon Co., Ltd. , Product name Asahi # 60G] 165 parts by weight, calcium carbonate [manufactured by Shiraishi Calcium Co., Ltd., product name Whiten SB] 30 parts by weight, softener [manufactured by Idemitsu Kosan Co., Ltd., product name Diana Process Oil TMPW-380] 70 Part by weight, 5 parts by weight of zinc white, and 1 part by weight of stearic acid were kneaded with a Banbury mixer [manufactured by Kobe Steel, Ltd.] having a capacity of 1.7 liters.

  As a kneading method, 3090E and polyethylene were 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 (P-4). This kneading was performed at a filling rate of 70%.

  Next, 401 parts by weight of this composition is wound around 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, made by Sanshin Chemical Industry Co., Ltd.) 2.0 parts by weight, accelerator CBS (Sansera-CM, made by Sanshin Chemical Industry Co., Ltd.) 1.0 part by weight, accelerator (Sanshin After adding 1.0 part by weight of Chemical Industrial Co., Ltd. (Sanfer R) and kneading for 10 minutes, the kneaded product was separated into a sheet. The sheet thus obtained was extruded using a 50 mm extruder [Mitsubishi Kogyo Co., Ltd.] at an extrusion rate of 2 m / min, crosslinked at 8 ° HAV oven at 230 ° C. for 4 minutes, and 2 mm thick and wide. A straight part of 2 cm was prepared as (A-4).

  Subsequently, EPDM [Mitsui Chemicals, trade name 4010], carbon black [Asahi Carbon Co., Ltd., trade name Asahi # 50] 85 parts by weight, softener [Idemitsu Kosan Co., Ltd., Product name Diana Process Oil TMPW-380] 20 parts by weight was kneaded with a 1.7 liter Banbury mixer [manufactured by Kobe Steel, Ltd.].

  As a kneading method, first, EPT was kneaded for 30 seconds, 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. This kneading was performed at a filling rate of 70%.

  Next, 205 parts by weight of this formulation was wound around 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), Sulfur 0.8 parts by weight, accelerator MBT [manufactured by Sanshin Chemical Industry Co., Ltd., trade name Suncera-M] 0.5 parts by weight, accelerator ZnBDC [manufactured by Sanshin Chemical Industry Co., Ltd., trade name Suncera-BZ] 0 After adding 3 parts by weight and kneading for 10 minutes, the kneaded product was separated into a sheet. (Q-4).

    A straight rubber part (A) having a thickness of 2 mm and a width of 2 cm was punched out into a JIS No. 3 dumbbell shape from a crosslinked rubber sheet. The dumbbell shape was cut in half at the center of the vote line, half of the dumbbell shape was set in an injection mold, and the extracted rubber composition was placed in the remaining half by injection molding. Was injection molded and cross-linked. The time required for cross-linking adhesion was determined as tc (90) of the sheet (Q-4), and measured at 180 ° C. according to JIS K6300 (1994). tc (90) was 3.5 minutes, and this time was determined as the time required for curing. Further, the dumbbell-shaped rubber was taken out after the injection molding, and a tensile test was conducted according to JISK6251 (1993), and the tensile strength at break was defined as the adhesive strength. The adhesive strength was 7 MPa.

  The compression set was 80%, whitening occurred in the anti-blooming test, and the sheet metal was contaminated in the sheet metal contamination test.

[Comparative Example 2]
Example 1 was used except that instead of the dispensing sheet (Q-4) of Comparative Example 1, a thermoplastic elastomer [Mitsui Chemicals Co., Ltd., Miralastomer (registered trademark) G751B] (R-5) was used. The same was done.
The time required for curing was 1 minute.

  The adhesive strength was 6 MPa. The compression set was 65%, whitening occurred in the bloom resistance test, and the sheet metal was contaminated in the sheet metal contamination test.

The sealing material of the present invention is an 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 a crosslinked product comprising a SiH group-containing compound (B) having at least two SiH groups in one molecule, a rubber composition (P) containing a catalyst (C), and crosslinked by a method other than sulfur vulcanization. Since it is characterized by being bonded to a crosslinked rubber (Q) or a thermoplastic elastomer (R), the bonded portion is difficult to peel off, and it has bloom resistance and environmental hygiene resistance (weather resistance). Resistance, environmental aging resistance, seal resistance, odor resistance, shortening the cross-linking adhesion time, and flexibility, water resistance, cold resistance of conventional EPDM-based sealing materials Can maintain sex Sheet - it is possible to obtain a sealing material. For example, door weather strip, trunk weather strip, luggage weather strip, roof side rail weather strip, sliding door weather strip, ventilator weather strip, sliding loop panel weather strip, front window weather strip, rear window weather strip, quarter window Weather Strip, Lock Pillar Weather Strip, Door Glass Outer Weather Strip, Door Glass Inner Weather Strip, Dam Wind Shield, Class Run Channel, Door Mirror Bracket, Seal Head Lamp, Seal Cowl Top, Door Weather Strip Sponge, Bonnet Weather Strip Sponge The trunk room weathers For automotive materials such as lip sponge, sunroof weather strip sponge, ventilator weather strip sponge, corner sponge, building gasket, air tight, joint material, door seal sponge, building material, hose protection sponge, cushion Examples include sponges, heat insulating sponges, insulation pipes, and automobile weather strip sponges.

Claims (6)

An 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 crosslinked product obtained from a rubber composition (P) containing at least two SiH group-containing compounds (B) and a catalyst (C), a crosslinked rubber (Q) crosslinked by a method other than sulfur vulcanization, Or a seal material obtained by bonding thermoplastic elastomer (R).

[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]. An 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 In a method other than sulfur vulcanization, a crosslinked product obtained from a rubber composition (P) containing at least two SiH group-containing compounds (B), a catalyst (C), and a reaction inhibitor (D). A seal material obtained by adhering a crosslinked rubber (Q) or a thermoplastic elastomer (R).

[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]. 3. The seal material 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 an 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 1.8 to 5 dl / g, and (iv) the branching index is in the range of 5 to 30. An ethylene / α-olefin having a structural unit derived from at least one non-conjugated polyene represented by the following general formula [I] or [II], wherein the crosslinked rubber (Q) crosslinked by a method other than sulfur vulcanization: A non-conjugated polyene random copolymer rubber (AA), a SiH group-containing compound (BB1) having at least two SiH groups in one molecule, and a rubber composition containing a catalyst (CC) are crosslinked. The seal material according to any one of claims 1 to 3, wherein the seal material is provided.

[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 crosslinked rubber (Q) crosslinked by a method other than sulfur vulcanization has an ethylene / α-olefin / having a structural unit derived from at least one non-conjugated polyene represented by the general formula [I] or [II]. The non-conjugated polyene random copolymer rubber (AA) and a rubber composition containing an organic peroxide (BB2) are cross-linked, and the sheet according to any one of claims 1 to 3, -Lu wood.   An 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 a SiH Only a crosslinking agent (BB) other than sulfur as a crosslinking agent is used as a crosslinking agent obtained from a rubber composition (P) containing a SiH group-containing compound (B) having at least two groups per molecule and a catalyst (C). A crosslinkable rubber composition (Q) containing a thermoplastic elastomer (R), and when the rubber composition (Q) is contacted, the rubber composition (Q) is crosslinked The seal material according to claim 1, wherein the seal material is manufactured by a method further including a step.