JP2012214582A - Cross-linkable rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cross-linkable rubber composition capable of improving both processability and non-staining properties and capable of sufficiently showing heat resistance and non-staining properties of a polyolefin based crosslinked rubber material by using a non-polar hydrocarbon based oil as a plasticizer.SOLUTION: The cross-linkable rubber composition is characterized by comprising at least 100 pts.wt. of component (A), 0.1-100 pts.wt. of component (B) and 10-1,000 pts.wt. of component (C), and after their mixing the viscosity is 0.01-10,000 Pa s at 25°C. Component (A) is a specific ethylene-α-olefin/nonconjugated polyene copolymer, component (B) is a hydrosilyl group containing compound having at least two hydrosilyl groups in the molecule, and component (C) is a non-polar hydrocarbon based oil.

Description

  The present invention relates to a rubber composition that can be crosslinked (vulcanized), and has excellent heat resistance and non-staining properties, and is suitable for electrical and electronic component materials including potting materials and sealing materials for electrical and electronic component materials. More particularly, the present invention relates to a crosslinkable (crosslinkable) rubber composition that is excellent in both processability and non-staining properties.

  In addition to heat resistance, non-contamination, and environmental hygiene, workability (low viscosity) is required for electrical / electronic component materials including potting materials and sealing materials for electrical / electronic component materials.

  On the other hand, a polyolefin-based crosslinked rubber material such as ethylene / propylene rubber is a material excellent in heat resistance and non-contamination, and is promising and suitable for these applications.

  However, workability (low viscosity) is required for electrical and electronic component materials including potting materials and sealing materials for electrical and electronic component materials. Polyolefin-based crosslinked rubber materials generally have high viscosity. Processability is insufficient.

  Therefore, in order to improve the processability (low viscosity) of the polyolefin-based crosslinked rubber material, a method of blending a plastic material such as paraffin oil is known, but it has reached the point where both processing and non-contamination are achieved. Not in.

  Furthermore, when a liquid resin such as silicone, which is mainly used, is blended in a potting material, a sealing material for electric / electronic component materials, etc., the non-contamination property decreases as the blending amount increases.

JP 2001-279027 A JP2008-88384

  Therefore, when using polyolefin-based cross-linked rubber materials for electrical and electronic component materials such as potting materials and sealing materials for electrical and electronic component materials, both workability and non-contamination can be improved sufficiently. It has become a challenge.

  The present invention uses a non-polar hydrocarbon-based oil as a plasticizer, in particular, an ethylene / α-olefin copolymer, thereby reducing the low molecular weight ethylene / α-olefin / non-conjugated polyene copolymer as a rubber component. It is based on the high compatibility with coalescence and the ability to improve both processability and non-contamination.

That is, the present invention comprises at least 0.1 to 100 parts by weight of component (B) and 10 to 1000 parts by weight of component (C) with respect to 100 parts by weight of component (A) at 25 ° C. after mixing. The present invention relates to a crosslinkable (vulcanizable) rubber composition characterized by having a viscosity of 0.01 Pa · s to 10000 Pa · s.
(A) having structural units derived from ethylene, an α-olefin having 3 to 20 carbon atoms, and at least one non-conjugated polyene represented by the following general formula [I] or [II], ) To (c) ethylene / α-olefin / non-conjugated polyene copolymer (a) The molar ratio of ethylene unit / α-olefin unit is 35/65 to 95/5.
(B) Iodine value of 0.5-50 g / 100 g (c) Intrinsic viscosity [η] measured with a decalin solution at 135 ° C. is 0.01-5 dl / g

[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]
(B) Hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule (C) Nonpolar hydrocarbon oil Further, the present invention is a nonpolar hydrocarbon in the above crosslinkable (vulcanizable) rubber composition. The system oil (C) has a dynamic viscosity at 40 ° C. of 1 to 10,000 mm ² / s, and relates to the above crosslinkable (vulcanizable) rubber composition.

  Furthermore, the present invention relates to the above crosslinkable (vulcanizable) rubber composition, wherein the nonpolar hydrocarbon oil is an ethylene / α-olefin oligomer.

  Furthermore, the present invention relates to a crosslinked rubber molded article obtained by crosslinking (vulcanizing) the rubber composition capable of being crosslinked (vulcanized).

  According to the present invention, a low molecular weight ethylene / α-olefin / non-conjugated polyene, which is a rubber component, is obtained by using a nonpolar hydrocarbon oil as a plasticizer, in particular, by using an ethylene / α-olefin copolymer. High compatibility with copolymer, can improve both processability and non-contamination, and sufficient heat resistance and non-contamination performance of polyolefin-based crosslinked rubber materials such as ethylene / propylene rubber It can be used for electrical and electronic component materials such as potting materials and encapsulants for electrical and electronic component materials, semiconductor chips such as silicon and compound semiconductors, and ceramics. Suitable as a base material for sealing and protecting resistors and capacitor chips, and as a base material for sealing and protecting electrodes and wiring Can be used.

  The crosslinkable (vulcanizable) rubber composition of the present invention is a composition containing the above component (A), component (B), and component (C).

  Each of the above components constituting the crosslinkable (vulcanizable) rubber composition of the present invention will be described.

Ethylene / α-olefin / non-conjugated polyene copolymer (A)
Component (A) has structural units derived from ethylene, an α-olefin having 3 to 20 carbon atoms, and at least one non-conjugated polyene represented by the following general formula [I] or [II]. It is an ethylene / α-olefin / non-conjugated polyene copolymer satisfying (a) to (c).

(A) The molar ratio of ethylene unit / α-olefin unit is 35/65 to 95/5.
(B) Iodine value of 0.5 to 50 (gram (g) / 100 gram (g))
(C) Intrinsic viscosity [η] measured with a decalin solution at 135 ° C. is 0.01 to 5 (dl / g)

[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 ethylene / α-olefin / non-conjugated polyene copolymer (A) used in the present invention is a copolymer of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, preferably a random copolymer. It is a polymer. 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 above 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 includes 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 .

As the norbornene compound represented by the above general formula [I] or [II], specifically,
5-methylene-2-norbornene, 5-vinyl-2-norbornene,
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-norbornene,
5- (3,4-dimethyl-4-pentenyl) -2-norbornene,
5- (3-ethyl-4-pentenyl) -2-norbornene,
5- (7-octenyl) -2-norbornene,
5- (2-methyl-6-heptenyl) -2-norbornene,
5- (1,2-dimethyl-5-hexesyl) -2-norbornene,
5- (5-ethyl-5-hexenyl) -2-norbornene,
5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene and the like.
Among these,
5-vinyl-2-norbornene, 5-methylene-2-norbornene,
5- (2-propenyl) -2-norbornene,
5- (3-butenyl) -2-norbornene,
5- (4-pentenyl) -2-norbornene,
5- (5-hexenyl) -2-norbornene,
5- (6-heptenyl) -2-norbornene,
5- (7-octenyl) -2-norbornene is preferred.
These norbornene compounds can be used alone or in combination of two or more.

  The ethylene / α-olefin / non-conjugated polyene copolymer (A) as described above has the following characteristics.

(A) Molar ratio of ethylene and α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin)
The ethylene / α-olefin / non-conjugated polyene copolymer (A) comprises (a) units derived from ethylene and (b) an α-olefin having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as “α-olefin”). Is contained in a molar ratio [(a) / (b)] of 35/65 to 95/5, preferably 50/50 to 90/10.

When this molar ratio is within the above range, a rubber composition capable of providing a crosslinked rubber molded article having excellent heat aging resistance, strength characteristics and rubber elasticity, and excellent cold resistance and processability is obtained.
(B) Iodine value The iodine value of the ethylene / α-olefin / non-conjugated polyene copolymer (A) is 0.5 to 50 (gram (g) / 100 gram (g))).

When the iodine value is less than 0.5 (g / 100 g), the crosslinking rate is slow, and when it exceeds 50 (g / 100 g), there are many long-chain branches, which leads to deterioration of workability, which is not preferable.
(C) Intrinsic viscosity [η] measured with a decalin solution at 135 ° C
The intrinsic viscosity [η] (measured with a decalin solution at 135 ° C.) of the ethylene / α-olefin / non-conjugated polyene copolymer (A) is 0.01 to 5 (dl / g). Especially preferably, it is 0.01-3 (dl / g), More preferably, it is 0.02-2.8 (dl / g). If the intrinsic viscosity [η] is less than 0.01, the workability may be deteriorated and the strength tends to be insufficient, and if it exceeds 5 (dl / g), the workability deteriorates.

In the present invention, as the ethylene / α-olefin / non-conjugated polyene copolymer (A), in addition to the physical properties of (i), (b) and (c), the molecular weight distribution (Mw / It is desirable to have Mn).
(D) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin / non-conjugated polyene copolymer (A) measured by GPC is 2 to 200, preferably 2 to 150, more preferably 2 to 100.

  When this molecular weight distribution (Mw / Mn) is within the above range, a rubber composition capable of providing a crosslinked rubber molded article having excellent processability and excellent strength characteristics is obtained.

The ethylene / α-olefin / non-conjugated polyene copolymer (A) used in the present invention has a polymerization temperature of 30 to 60 ° C. in the presence of a catalyst containing the following compounds (D) and (E) as main components. Especially 30 to 59 ° C., polymerization pressure 4 to 50 kgf / cm ² , particularly 5 to 40 kgf / cm ² , molar ratio of non-conjugated polyene and ethylene supplied (non-conjugated polyene / ethylene) 0.01 to 0.2 Obtained by copolymerization, particularly random copolymerization of ethylene, an α-olefin having 3 to 20 carbon atoms, and a terminal vinyl group-containing norbornene compound represented by the above general formula [I] or [II]. It is done. The copolymerization is preferably carried out in a hydrocarbon medium.

(D) a soluble vanadium compound represented by VO (OR) _n X _3-n (wherein R is a hydrocarbon group, X is a halogen atom, and n 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 (D) is a component that is soluble in the hydrocarbon medium of the polymerization reaction system. Specifically, the general formula VO (OR) aXb or V (OR) cXd (wherein R is a hydrocarbon group) 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4), or electron donation thereof A body adduct can be given as a representative example.

More specifically, VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) Cl ₂ , VO (On-C ₄ H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₃ , VCl ₄ , VOCl ₃ , VO (On-C ₄ H ₉ ) ₃ , VCl ₃ · 2OC ₆ H ₁₂ OH, etc. be able to.
(E) An organoaluminum compound represented by R′m AlX ′ _3-m (R ′ is a hydrocarbon group, X ′ is a halogen atom, and m is an integer of 1 to 3). the E), specifically, triethylaluminum, tri-butyl aluminum, tri-alkyl aluminum such as tri-isopropyl aluminum; R ¹ _0; alkyl sesquichloride alkoxides such as ethylaluminum sesquichloride ethoxide; dialkylaluminum alkoxides such as diethylaluminum ethoxide _.5 partially alkoxylated alkylaluminum having an average composition represented by Al (OR ¹ ) _0.5 ; dialkylaluminum halides such as diethylaluminum chloride; alkylaluminiums such as ethylaluminum sesquichloride Partially halogenated alkylaluminums such as alkyl aluminum dihalides such as Musesquihalide; Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as dialkylaluminum hydrides such as diethylaluminum hydride; Ethylaluminum ethoxy Mention may be made of partially alkoxylated and halogenated alkylaluminums such as chloride.

In the present invention, among the above compound (D), a soluble vanadium compound represented by VOCl ₃ and among the above compound (E), Al (OC ₂ H ₅ ) ₂ Cl / Al ₂ (OC ₂ H ₅ ) ₃ Cl _When a blend of 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. The ethylene / α-olefin / non-conjugated polyene copolymer (A) is preferable because it is obtained.

  In addition, a so-called metallocene catalyst is also used as a catalyst used in the above copolymerization, and a catalyst used in producing an ethylene / α-olefin copolymer suitable as a nonpolar hydrocarbon oil described later. Can also be used.

  The ethylene / α-olefin / non-conjugated polyene copolymer (A) used in the present invention may be graft-modified with a polar monomer such as an unsaturated carboxylic acid or a derivative thereof (for example, an acid anhydride or ester). Good.

  Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and bicyclo (2,2,1) hept-2-ene. And -5,6-dicarboxylic acid.

  Specific examples of unsaturated carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo (2,2,1) hept-2-ene-5,6- And dicarboxylic acid anhydride. Among these, maleic anhydride is preferable.

  Specific examples of the unsaturated carboxylic acid ester include methyl acrylate, ethyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, and bicyclo (2,2,1) hept-2-ene-5,6. -Dimethyl dicarboxylate etc. are mentioned. Among these, methyl acrylate and ethyl acrylate are preferable.

  The above-mentioned graft modifiers (graft monomers) such as unsaturated carboxylic acids are used singly or in combination of two or more, and in any case, the ethylene / α-olefin / non-conjugated before the graft modification described above. The graft amount is preferably 0.1 mol or less per 100 g of the polyene copolymer (A).

  When the ethylene / α-olefin / non-conjugated polyene copolymer (A) having the graft amount in the above range is used, it is possible to provide a crosslinked rubber molded product having excellent cold resistance. Is obtained.

  The graft-modified ethylene / α-olefin / non-conjugated polyene copolymer (A) is obtained by radical initiation of the above-mentioned unmodified ethylene / α-olefin / non-conjugated polyene copolymer and an unsaturated carboxylic acid or a derivative thereof. It can be obtained by reacting in the presence of an agent.

  This grafting reaction can be performed as a solution or in a molten state. When the graft reaction is performed in a molten state, it is most efficient and preferable to perform it continuously in an extruder.

  Specific examples of the radical initiator used in the graft reaction include dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, and di-t-butylperoxy-3,3,5-trimethylcyclohexane. Peroxyesters such as t-butyl peroxyacetate; ketone peroxides such as dicyclohexanone peroxide; and mixtures thereof. Among them, organic peroxides having a half-life of 1 minute at a temperature in the range of 130 to 200 ° C. are preferable, and in particular, dicumyl peroxide, di-t-butyl peroxide, di-t-butyl peroxide-3,3, Organic peroxides such as 5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide, and t-butyl hydroperoxide are preferred.

  In addition, polar monomers other than unsaturated carboxylic acids or derivatives thereof (for example, acid anhydrides and esters) include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, and epoxy group-containing ethylenically unsaturated compounds. , Aromatic vinyl compounds, vinyl ester compounds, vinyl chloride and the like.

Hydrosilyl group-containing compound (B) having at least two hydrosilyl groups in one molecule
The hydrosilyl group-containing compound (B) having at least two hydrosilyl groups used in the present invention reacts with the ethylene / α-olefin / non-conjugated polyene copolymer (A) to act as a crosslinking agent. The hydrosilyl group-containing compound (B) is not particularly limited in its molecular structure, and can be used in a conventionally produced resinous material such as a linear, cyclic, branched structure or three-dimensional network structure. It is necessary that one molecule contains a hydrogen atom directly bonded to at least two silicon atoms, that is, a SiH group.

As the hydrosilyl group-containing compound (B), a compound represented by the general composition formula R ⁴ _b H _c S _i O _{(4-bc) / 2} can be used.

In this 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 R ¹ . 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.

  The hydrosilyl group-containing compound (B) is preferably an organohydrogenpolysiloxane having preferably 2 to 1000, particularly preferably 2 to 300, most preferably 3 to 200 silicon atoms in one molecule. Specifically, siloxane oligomers such as 1,1,3,3-tetramethyldisiloxane; molecular chain both ends trimethylsiloxy group-capped methylhydrogen polysiloxane, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane methylhydrogen Siloxane copolymer, molecular chain both-end silanol-blocked methylhydrogen polysiloxane, molecular chain both-end silanol-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both-end dimethylhydrogensiloxy group-blocked Dimethylpolysiloxane, both ends of molecular chain Methyl hydrogen siloxy group methylhydrogenpolysiloxane capped at both molecular chain terminals blocked with dimethylhydrogensiloxy groups dimethylsiloxane-methylhydrogensiloxane silicone consisting of siloxane copolymers - Nrejin and the like.

  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, propyl group, phenyl group, trifluoropropyl group. And the like.

(CH ₃ ) ₃ SiO — (— SiH (CH ₃ ) —O—) _d —S _i (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.
_{(CH 3) 3 S i O} - (- S i (CH 3) 2 -O-) e - (- S i H (CH 3) -O-) f -S i (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 further, in the following formula, a part or all of the methyl group is ethyl, propyl, phenyl, trifluoropropyl. And a compound substituted with a group.

_{HOS i (CH 3) 2 O} - (- S i H (CH 3) -O-) 2 -S i (CH 3) 2
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, in the following formula, a part or all of the methyl group is ethyl, propyl, phenyl Group, a compound substituted with a trifluoropropyl group, and the like.

_{HOS i (CH 3) 2 O} - (- Si (CH 3) 2 -O-) e - (- S i H (CH 3) -O-) f -S i (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 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.

_{HS i (CH 3) 2 O} - (- S i (CH 3) 2 -O-) e -S i (CH 3) 2 H
[E in the formula is an integer of 1 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.

_{HS i (CH 3) 2 O} - (- S i H (CH 3) -O-) e -S i (CH 3) 2 H
[E in the formula is an integer of 1 or more. ]
Examples of the dimethylhydrogensiloxy group-blocked dimethyl siloxane / methyl hydrogen siloxane copolymer having both ends of the molecular chain include, for example, a compound represented by the following 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.

_{HS i (CH 3) 2 O} - (- S i (CH 3) 2 -O-) e - (- S i H (CH 3) -O-) h -S i (CH 3) 2 H
[E and h in the formula 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 the like 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.

  Said hydrosilyl group containing compound (B) can be used individually or in mixture of 2 or more types arbitrarily selected in arbitrary ratios.

  The hydrosilyl group-containing compound (B) is generally 0.5 to 100 parts by weight, preferably 1 to 70 parts by weight, more preferably 100 parts by weight of the ethylene / α-olefin / nonconjugated polyene copolymer (A). Is 1-30 parts by weight.

  When the hydrosilyl group-containing compound (B) is used in a proportion within this range, a rubber composition capable of forming a crosslinked rubber molded article having excellent compression set resistance, moderate crosslinking density, and excellent strength and elongation properties. can get. Use in excess of 100 parts by weight is not preferable because it is disadvantageous in cost.

Specific examples of preferred hydrosilyl group-containing compounds include ((C ₆ H ₅ ) Si (OSi (CH ₃ ) ₂ H) ₃ ), (C ₆ H ₅ ) ₂ Si (OSi (CH ₃ ) ₂ H). ₂ , Si (CH ₃ ) ₃ O (SiH (CH ₃ ) O) ₆ Si (CH ₃ ) ₂ O (SiH (C ₆ H ₅ ) O) Si (CH ₃ ) ₂ OCH _{3 and the} like.

Nonpolar hydrocarbon oil (C)
The nonpolar hydrocarbon oil used in the present invention is preferably one having a dynamic viscosity of 1 to 10,000 mm ² / s at 40 ° C.

An oil having a kinematic viscosity at 40 ° C. of less than 1 mm ² / s has many low molecular weight components that are likely to volatilize, so that the heat resistance may be deteriorated. On the other hand, when it exceeds 10,000 mm ² / s, the high molecular weight component increases, the viscosity becomes insufficient, and the effect of improving workability decreases.

  In the present invention, as the nonpolar hydrocarbon oil, the nonpolar hydrocarbon oil composed of an ethylene / α-olefin copolymer is compatible with the ethylene / α-olefin / nonconjugated polyene copolymer (A). Is particularly preferred.

  A nonpolar hydrocarbon-based oil comprising such an ethylene / α-olefin copolymer is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. As the α-olefin, propylene, 1- Butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1 -Hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene linear α-olefin, 4-methyl-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, Examples include branched α-olefins such as 6-methyl-1-undecene and 6,8-dimethyl-1-decene. These are α-olefins, and one or more of these are used as necessary. Such an ethylene-α-olefin copolymer is particularly preferably a random copolymer. Generally, the ethylene structural unit is 5 mol% to 95 mol%, and the α-olefin structural unit is 95 mol%. % To 5 mol% (the total of ethylene and α-olefin is 100 mol%).

  Further, such an ethylene-α-olefin copolymer generally has a number average molecular weight (Mn) of 100 to 30000, preferably 100 to 20000.

  When the number average molecular weight (Mn) is less than 100, low molecular weight components that are likely to volatilize increase, and heat resistance may deteriorate. On the other hand, when the number average molecular weight (Mn) exceeds 30000, the high molecular weight component increases, and the effect of improving workability decreases.

  Further, the molecular weight distribution (Mw / Mn) is generally 1.1 to 3, and 1.1 to 2.5 is preferable among them.

  When the molecular weight distribution (Mw / Mn) exceeds 3, generally, low molecular weight components that are likely to volatilize increase, and heat resistance may be deteriorated.

  Furthermore, the content rate of the unsaturated group at the molecular fragment end in such an ethylene-α-olefin copolymer is 10% or less, preferably 5% or less, more preferably 1% or less.

  As methods for producing these ethylene-α-olefin copolymers, JP-A-3-179005, JP-A-3-19396, JP-A-6-122718, JP-A-8-239414, There exists a method using the catalyst used when manufacturing an alpha-olefin type polymer as described in Kaihei 10-087716 and Unexamined-Japanese-Patent No. 2000-212194.

Specifically, for example, the transition metal compound is a Group 4 transition metal compound (X) and (Y)
(Y-1) an organometallic compound,
(Y-2) an organoaluminum compound,
(Y-3) an organoaluminum oxy compound,
(Y-4) a compound that reacts with the Group 4 transition metal compound (A) to form an ion pair,
Can be obtained by copolymerizing ethylene and an α-olefin in the presence of an olefin polymerization catalyst comprising at least one compound selected from

  Specific examples of the transition metal compound (X) include titanium tetrachloride, dimethyl titanium dichloride, tetrabenzyl titanium, tetrabenzyl zirconium, and tetrabutoxy titanium. Examples of non-crosslinkable or crosslinkable metallocene compounds include transition metal compounds belonging to Group 4 of the periodic table having a cyclopentadienyl skeleton. Examples of ligands having a cyclopentadienyl skeleton include cyclopentadienyl skeleton. Examples thereof include a group, an alkyl-substituted cyclopentadienyl group, an indenyl group, an alkyl-substituted indenyl group, a 4,5,6,7-tetrahydroindenyl group, a fluorenyl group, and an alkyl-substituted fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. When two or more of these ligands having a cyclopentadienyl skeleton are included, among the ligands having two cyclopentadienyl skeletons, an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, etc. It may be connected via. Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group; a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, and a tetramethylcyclopentadienyl group. , Pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopenta Alkyl-substituted cyclopentadienyl groups such as dienyl group and hexylcyclopentadienyl group; indenyl group; 4,5,6,7-tetrahydroindenyl group, 2-methylindenyl, tetrahydroindenyl, 2-methyltetrahydro Indenyl, 2, , 4-trimethyl tetrahydroindenyl, fluorenyl; benzofluorenyl, dibenzo fluorenyl, octahydro dibenzo fluorenyl, and the like can be exemplified octamethyloctahydrodibenzofluorenyl like.

  Specifically, bis (butylcyclo) containing cyclopentadienyl trichloride, cyclopentadienyl zirconium trichloride, bis (cyclopentadienyl) titanium dichloride, (n-butylcyclopentadienyl) zirconium dichloride, and the like. Pentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium dichloride including bis (diethylcyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (1-indenyl) Titanium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, isopropylidene (methyl-tert-butylcyclopentadienyl) ) (3,6-di-tert-butylfluorenyl) zirconium dichloride.

  Examples of the ethylene-α-olefin copolymer thus produced include those commercially available from Mitsui Chemicals under the trade name “Lucanto” (registered trademark).

  The proportion of these nonpolar hydrocarbon oils, particularly ethylene-α-olefin copolymer, in the composition is 10 with respect to 100 parts by weight of ethylene / α-olefin / nonconjugated polyene copolymer (A). -1000 weight part, Preferably it is 10-800 weight part, More preferably, it is 10-500 weight part.

  When these nonpolar hydrocarbon-based oils, particularly ethylene-α-olefin copolymers are used in a proportion within this range, they have excellent compression set resistance, moderate crosslinking density, and excellent strength and elongation properties. A rubber composition capable of forming a rubber molded body is obtained.

Catalyst (F)
In the composition of the present invention, the catalyst (F) used as an optional component is an addition reaction catalyst, and the alkenyl group-containing hydrosilyl group-containing compound (A) component of the ethylene / α-olefin / nonconjugated polyene copolymer (A) ( There is no particular limitation as long as it promotes the addition reaction of B) with a hydrosilyl group (alkene hydrosilylation reaction). For example, an addition reaction catalyst comprising a platinum group element such as a platinum catalyst, a palladium catalyst, or a rhodium catalyst. (Group 8 metal catalyst such as Group 8 metal, Group 8 metal complex, Group 8 metal compound, etc.) in the periodic table can be mentioned, and among them, platinum catalyst is preferable.

  Suitable platinum catalysts may be those known for use in addition-curing curing, such as the finely powdered platinum metal catalyst described in US Pat. No. 2,970,150, US Pat. 823,218, chloroplatinic acid catalyst, US Pat. No. 3,159,601 and US 159,662 complex compounds of platinum and hydrocarbons, US Pat. Complexes of chloroplatinic acid and olefins described in US Pat. No. 3,516,946, platinum described in US Pat. No. 3,775,452 and US Pat. No. 3,814,780 And complex compounds with vinyl siloxane.

  More specifically, examples include platinum alone (platinum black), chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, or a carrier such as alumina or silica on which a platinum carrier is supported. They can be used alone or in admixture of two or more selected at an arbitrary ratio.

  The amount of the hydrosilicon crosslinking catalyst (F) is 0.1 to 100,000 ppm by weight based on the ethylene / α-olefin / non-conjugated polyene copolymer (A). Preferably it is 0.1-50000 weight ppm, More preferably, it is 0.1-30000 weight ppm. If it is 0.1 weight ppm or less, the crosslinking rate is slow, and if it is used in a proportion exceeding 100,000 weight ppm, it is not preferable because it is disadvantageous in terms of cost. When the hydrosilicon crosslinking catalyst (F) is used in a proportion within the above range, a rubber composition capable of forming a vulcanized rubber molded article having a moderate crosslinking density and excellent strength properties and elongation properties can be obtained.

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

Reaction inhibitor (G)
Examples of the reaction inhibitor (G) used as an optional component together with the catalyst (F) in the present invention include benzotriazole, ethynyl group-containing compounds (for example, ethynylcyclohexanol, 3,7,11-trimethyl-3-hydroxy- 1-dodecine, 3,7,11-triethyl-3-hydroxy-1-dodecine, 4-ethyl-1-octin-3-ol, etc.), 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 ′, N′— Tetraallyl-p-phthalic acid diamide, etc.), sulfur, phosphorus, nitrogen, amine compounds, sulfur compounds, phosphorus compounds, tin, tin compounds, tetramethyltetravinyl Cyclotetrasiloxane, Haidoropa - organic peroxides, such as oxide. The crosslinking reaction between the alkenyl group of the ethylene / α-olefin / non-conjugated polyene copolymer (A) and the hydrosilyl group of the (B) hydrosilyl group-containing compound is suppressed. Suppression of this crosslinking reaction is necessary to stabilize the workability during kneading and molding.

  The reaction inhibitor (G) is 0 to 50 parts by weight, usually 0.01 to 50 parts by weight, preferably 0.01 to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A). -30 parts by weight, more preferably 0.01-20 parts by weight, still more preferably 0.01-10 parts by weight, particularly preferably 0.01-5 parts by weight.

  When the reaction inhibitor (G) is used in a proportion of 0.01 parts by weight or less, a rubber composition having a high crosslinking speed and excellent productivity of a crosslinked rubber molded product can be obtained. Use of the reaction inhibitor (G) in a proportion exceeding 50 parts by weight is not preferable because it is disadvantageous in terms of cost.

  Other components The crosslinkable rubber composition according to the present invention can be used even in an uncrosslinked state. It can be demonstrated.

  In the crosslinkable rubber composition according to the present invention, conventionally known rubber reinforcing agents, inorganic fillers, softeners, anti-aging agents, processing aids, vulcanization accelerators, depending on the intended use of the cross-linked product. 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.

  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 those that have been surface-treated with carbon black such as SRF, GPF, FEF, HAF, ISAF, SAF, FT, and MT, and silane coupling agents. Carbon black, finely divided silicic acid, silica and the like.

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 based on 100 parts by weight of the ethylene / α-olefin / nonconjugated polyene copolymer (A). , Up to 300 parts by weight, preferably up to 200 parts by weight.

  Specific examples of these inorganic fillers 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 use, the compounding quantity of an inorganic filler is usually 100 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer (A). , Up to 300 parts by weight, preferably up to 200 parts by weight.

  Examples of amine-based antioxidants used in the present invention include diphenylamines and phenylenediamines. Specific examples of diphenylamines include p- (p-toluenesulfonylamide) -diphenylamine, 4,4 ′-(α, α-dimethylbenzyl) diphenylamine, 4,4′-dioctyl diphenylamine, diphenylamine and acetone. High temperature reaction product of diphenylamine with acetone, low temperature reaction product of diphenylamine with aniline and acetone, reaction product of diphenylamine with diisobutylene, octylated diphenylamine, dioctylated diphenylamine, p, p ' -Dioctyl diphenylamine, alkylated diphenylamine and the like.

  Specific examples of phenylenediamines include N, N′-diphenyl-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, and N, N′-di-2-naphthyl-p-. Phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N, N′-bis (1- Methylheptyl) -p-phenylenediamine, N, N′-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N′-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, phenylhexyl-p-phenylenediamine, phenyloct Examples include p-phenylenediamines such as til-p-phenylenediamine.

  Among these, 4,4 ′-(α, α-dimethylbenzyl) diphenylamine and N, N′-di-2-naphthyl-p-phenylenediamine are particularly preferable. These compounds can be used alone or in combination of two or more.

Specific examples of the hindered phenol anti-aging agent used in the present invention include (1) 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenylbutane,
(2) 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol),
(3) 2,2-thiobis (4-methyl-6-t-butylphenol),
(4) 7-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate,
(5) Tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate methane,
(6) pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
(7) Triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate],
(8) 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],
(9) 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine,
(10) Tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate,
(11) 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate],
(12) N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy) -hydrocinnamide,
(13) 2,4-bis [(octylthio) methyl] -o-cresol,
(14) 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate-diethyl ester,
(15) Tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane,
(16) Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid ester,
(17) 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4-8,10- And tetraoxaspiro [5,5] undecane. Of these, the phenolic compounds (5) and (17) are particularly preferable.

  As the sulfur-based anti-aging agent used in the present invention, a sulfur-based anti-aging agent usually used for rubber is used. Specifically, 2-mercaptobenzoimidazole, zinc salt of 2-mercaptobenzoimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptomethylbenzimidazole, 2-mercaptomethylimidazole Imidazole anti-aging agents such as zinc salts; dimyristyl thiodipropionate, dilauryl thiodipropionate, distearyl thiodipropionate, ditridecyl thiodipropionate And aliphatic thioether antioxidants such as pentaerythritol tetrakis- (β-lauryl-thiopropionate). Among these, 2-mercaptobenzoimidazole, zinc salt of 2-mercaptobenzoimidazole, 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 and palmitic acid And esters of higher fatty acids such as lauric acid.

  Such a processing aid is usually 10 parts by weight or less, preferably 100 parts by weight or less, based on a total amount of 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A) and the hydrosilyl group-containing compound (B). Is used at a ratio of 5 parts by weight or less, but it is desirable to appropriately determine the optimum amount according to the required physical property values.

  In the present invention, in addition to the catalyst (F) 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 copolymer (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; diallyl phthalate and triallyl cyanurate. And allyl compounds such as maleimide compounds and 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.

  Specific examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite; N, N′-dimethyl-N, N′-dinitrosotephthalamide Nitroso compounds such as N, N'-dinitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonyl hydrazide Sulfonylhydrazide compounds such as toluenesulfonylhydrazide, p, p′-oxybis (benzenesulfonylhydrazide), diphenylsulfone-3,3′-disulfonylhydrazide; calcium azide, 4,4-diphenyldisulfonylazide, p-toluenesulfuride Azide compounds such Runiruajido the like.

These foaming agents are 0.5 to 30 parts by weight, preferably 100 to 30 parts by weight, preferably 100 parts by weight of the total amount of the ethylene / α-olefin / non-conjugated polyene copolymer (A) and the hydrosilyl group-containing compound (B). It is used at a ratio of 1 to 20 parts by weight. When the foaming agent is used in the above ratio, a foam having a specific gravity of 0.03 to 0.8 g / cm ³ can be produced, but the optimum amount can be appropriately determined according to the required physical property values. desirable.

  Moreover, you may use a foaming adjuvant together with a foaming agent as needed. The foaming auxiliary agent acts to lower the decomposition temperature of the foaming agent, accelerate the decomposition, and make the bubbles uniform. Examples of such foaming assistants include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid, urea, and derivatives thereof.

  These foaming assistants are used in a proportion of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene copolymer (A). However, it is desirable to appropriately determine the optimum amount according to the required physical property value.

  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 rubbers include isoprene-based rubbers such as natural rubber (NR) and isoprene rubber (IR), 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).

Preparation of Rubber Composition and Crosslinked Rubber Molded Article As described above, the crosslinkable rubber composition according to the present invention can be used without being crosslinked, but the crosslinked rubber molded article or the crosslinked rubber foam molded article can be used. When used as such a cross-linked product, the characteristics can be exhibited most.

  In order to produce a crosslinked product from the crosslinkable rubber composition according to the present invention, an uncrosslinked compounded rubber is prepared once in the same manner as when ordinary rubber is vulcanized (crosslinked). Cross-linking may be carried out after forming the desired shape.

  As a crosslinking method, either a method of heating using a crosslinking agent (hydrosilyl group-containing compound (B)) or a method of irradiation with light, γ rays or electron beams may be adopted.

  First, the crosslinkable rubber composition according to the present invention is prepared, for example, by the following method.

  That is, the crosslinkable rubber composition according to the present invention is obtained by using an internal mixer (closed mixer) such as a banbury mixer, a kneader, or an intermix to produce ethylene / α-olefin / non- Conjugated polyene copolymer (A), nonpolar hydrocarbon oil (C) and, if necessary, additives such as rubber reinforcing agents, inorganic fillers and softeners, preferably at a temperature of 80 to 170 ° C. for 3 to 10 After kneading for a minute, using a roll such as an open roll, or a kneader, the hydrosilyl group-containing compound (B), and optionally a catalyst (F), a reaction inhibitor ( G), a vulcanization accelerator, a crosslinking aid, a foaming agent, and a foaming aid may be additionally mixed, and preferably kneaded for 1 to 30 minutes at a roll temperature of 80 ° C. or less, and then prepared by dispensing. it can.

  In the present invention, the ethylene / α-olefin / non-conjugated polyene copolymer (A), nonpolar hydrocarbon oil (C), rubber reinforcing agent, inorganic filler and the like can be kneaded at a high temperature. When the hydrosilyl group-containing compound (B) and the catalyst (F) are kneaded at the same time at a high temperature, the hydrosilyl group-containing compound (B) and the catalyst (F) may be combined. When adding simultaneously, it is preferable to knead | mix at 80 degrees C or less. When one component is added among the hydrosilyl group-containing compound (B) and the catalyst (F), they can be kneaded even at a high temperature exceeding 80 ° C. In some cases, it is preferable to use cooling water against heat generated by kneading.

  Further, when the kneading temperature in the internal mixers is low, the ethylene / α-olefin / non-conjugated polyene copolymer (A), the hydrosilyl group-containing compound (B), the nonpolar hydrocarbon oil (C) In addition to rubber reinforcing agents, inorganic fillers, softeners, etc., anti-aging agents, colorants, dispersants, flame retardants, foaming agents and the like may be kneaded simultaneously.

  The crosslinkable rubber composition according to the present invention prepared as described above is obtained by various molding methods using an extrusion molding machine, a calender roll, a press, an injection molding machine, a transfer molding machine, and the like. It can be molded into the intended shape, and can be cross-linked by introducing the molding into the vulcanizing tank at the same time as molding or in the vulcanizing tank. A crosslinked product is obtained by heating at a temperature of 120 to 270 ° C. for 1 to 30 minutes, or by irradiating light, γ-rays or electron beams by the method described above. 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 vulcanizing tank, a heating tank such as hot air, a glass bead fluidized bed, UHF (ultra-high frequency electromagnetic wave), or a steam can be used.

  Further, when the low molecular weight ethylene / α-olefin / non-conjugated polyene copolymer (A) is used, since the copolymer (A) is in a liquid state, the hydrosilyl group-containing compound (B) in the liquid state. , Mix nonpolar hydrocarbon oil (C), mix catalyst (F), reaction inhibitor (G), foaming agent, foaming aid as needed, and pour into mold of desired shape at room temperature It can be cross-linked.

   A cross-linked rubber molded product obtained from the cross-linkable rubber composition according to the present invention comprises: an automobile weather strip; an automobile hose, a water supply hose, a gas hose, and other hoses; Anti-vibration rubber such as vibration rubber, anti-vibration rubber for railways, anti-vibration rubber for industrial machines, seismic isolation rubber for constructions; belts for power transmission belts, conveyor belts, etc .; -Seal materials such as seal materials; foams such as automobile weather strip sponges, architectural seal sponges, other hose protection sponges, cushion sponges, heat insulation sponges, and insulation pipes; Wire joints, electrical insulation parts, semiconductive rubber parts; rolls for office automation equipment, industrial rolls; waterproofing sheets for construction, waterproofing sheets for civil engineering; rain gear, rubber bands, shoes, rubber gloves, Household items such as latex and golf balls; Plastic reforming, thermoplastic elastomers - for, for water crosslinked rubber, thermoplastic resin modifying agents, used widely in applications such as for engineering plastics modification.

  Also, paints, adhesives, tape products, heat dissipation materials, electromagnetic shielding, infusion caps, adhesives, coating materials, stress absorbers, solar cell sealing materials, LED sealing materials, Li battery gaskets, fuel It can also be used for battery gaskets, wire waterproofing materials, dental impression materials, etc.

  If the rubber composition of the present invention is used as a surface sealing material or a peripheral edge sealing material of a solar cell, it is possible to seal at room temperature, water resistance (moisture resistance), rubber elasticity, fillability, It has excellent adhesion (adhesion) properties and can achieve sealing performance higher than conventional.

  If the rubber composition of the present invention is used for the in-cell cavity / sealing part or the case sealing part of the organic thin film solar cell, the case sealing can be performed in a process integrated with the case sealing, and process loss can be reduced.

  If the composition of the present invention is used as a sealing material for a dye-sensitized solar cell, room temperature crosslinking is possible and water resistance can be improved.

  If the rubber composition of the present invention is used for materials used for water-stop treatment of electric wires and cables, potting materials used for sealing electronic parts, sealing agents used for architectural sealing applications, and adhesive layers used for adhesive tape applications In addition to room temperature crosslinking, water resistance can be improved.

  If the rubber composition of the present invention is used as a binder for heat dissipation materials, electromagnetic shielding materials, antistatic materials, conductive materials, ceramic capacitors, or paint binders, room temperature crosslinking, solventlessness, and improved water resistance are possible. It becomes.

  If the rubber composition of the present invention is used as a resin used for gaskets and rubber packings, it is possible to lower the processing viscosity and to impart flexibility and improve sealing performance.

  When the rubber composition of the present invention is used as the resin used for the vibration control material and the damping member, in-situ processing (coating), room temperature crosslinking, and solvent-free are possible.

  If the rubber composition of the present invention is used as a resin used for a high resilience material, in-situ processing (coating), room temperature crosslinking, solventless and water resistance can be improved.

  If the rubber composition of the present invention is used as a resin used for a dental impression material, it is easy to remove the impression because it has a large elastic strain and can be easily released by controlling the adhesiveness.

  By using the rubber composition of the present invention as a polyolefin-based synthetic rubber material used for rubber rolls for industrial and office equipment, moldability can be improved and high productivity can be exhibited.

  By using the rubber composition of the present invention as a material used for the rubber hose, moldability can be improved and high productivity can be exhibited. If the rubber composition of the present invention is used as a resin lens, both good moldability and dimensional stability can be achieved.

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

The composition, iodine value, intrinsic viscosity [η], and molecular weight distribution (Mw / Mn) of the copolymers used in Examples and Comparative Examples were measured or determined by the following methods.
(1) Composition of copolymer The composition of the copolymer was measured by ¹³ C-NMR method.
(2) Iodine value of copolymer (g / 100g)
The iodine value of the copolymer was determined by a titration method.
(3) Intrinsic viscosity [η]
The intrinsic viscosity [η] of the copolymer was measured in 135 ° C decalin.
(4) Viscosity evaluation Using an E-type viscometer (RE-105U) manufactured by Toki Sangyo Co., Ltd., a plate (angle: 1 ° × R24 mm (mm) or 3 ° × R14 mm) Torr (mm), rotational speed: 0.1 to 50 rpm, sample amount: 0.6 to 1.0 gram (g), and the value showing the same value for 30 seconds or more was taken as the viscosity.

The case where the viscosity after mixing falls within the range of 0.01 Pa · s to 10000 Pa · s was marked as ◯.
(5) Crosslinkability evaluation The rubber composition heated at 150 ° C. for 10 to 60 minutes was grasped with a filter paper, and the presence or absence of deposits on the filter paper surface was confirmed. The case where there was no deposit on the surface of the filter paper was marked with ◯.
(6) Consistency evaluation The penetration of the crosslinked rubber composition was measured. The measurement was performed using an apparatus based on JIS K 2207, and the penetration was measured after 5 seconds. A case where the needle penetrates 1.5 millimeters (mm) or more was marked as ◯.
(7) Volatility evaluation The thermal decomposition temperature of the crosslinked rubber composition was evaluated. As a measuring device, TGA-51 manufactured by Shimadzu Corporation was used. A predetermined amount of sample is weighed on an aluminum pan attached to TGA-51 and placed on the balance of the apparatus. After raising the temperature from room temperature to 150 ° C. in an air atmosphere, heating is performed for 60 minutes to perform pyrolysis behavior (weight) Decrease) was measured. A case where the weight loss by heating at 150 ° C. for 60 minutes was 1% by weight or less was evaluated as ◯.
(8) Bleed-out evaluation The surface of the crosslinked rubber composition was visually observed to confirm whether oil was bleeding out on the surface. The case where there was no oil bleed was marked with ◯.

[Example 1]
Composition of evaluation result list of ethylene / α-olefin / non-conjugated polyene random copolymer, hydrosilyl group-containing compound (B-1, trade name: X93-916), nonpolar hydrocarbon oil (C), plasticizer Weighed according to composition. The weighed sample was stirred for 300 s or more using THINKY Awatori Ren Taro (AR-250).
A Pt catalyst was added to the rubber composition, and the mixture was stirred for 60 s or longer using THINKY Awatori Rentaro (AR-250). Using a vacuum pump, defoaming was performed for 5 minutes or more under the condition of> 1 cmHg. It moved to the container and bridge | crosslinked by the heating for 150 degreeC x 10 minutes.

[Example 2, Comparative Example 1 and Comparative Example 2]
The procedure was the same as in Example 1 except that the blending amounts shown in Example 1 were changed as shown in Table 1. The results are shown in Table 1.

  A cross-linked rubber molded product obtained from the cross-linkable rubber composition according to the present invention includes an automobile weather strip; an automobile hose, a water supply hose, a gas hose, and other hoses; Anti-vibration rubber, anti-vibration rubber for railways, anti-vibration rubber for industrial machinery, anti-vibration rubber for construction, etc .; belts for transmission belts, conveyor belts, etc .; cups and seals for automobiles, industrial machinery Seal materials such as seal materials; weather strip sponges for automobiles, seal seal sponges for buildings, foams such as sponges for hose protection, sponges for cushions, heat insulation sponges, and insulation pipes; , Wire joints, electrical insulation parts, semiconductive rubber parts; rolls for office automation equipment, industrial rolls; waterproofing sheets for construction, waterproofing sheets for civil engineering; rain gear, rubber bands, shoes, rubber gloves , Latex, golf balls and other household items Plastic modification, a thermoplastic elastomer - for, for water crosslinked rubber, thermoplastic resin modifying agents, used widely in applications such as for engineering plastics modification.

  Also, paints, adhesives, tape products, heat dissipation materials, electromagnetic shielding, infusion caps, adhesives, coating materials, stress absorbers, solar cell sealing materials, LED sealing materials, Li battery gaskets, fuel It can also be used for battery gaskets, wire waterproofing materials, dental impression materials, etc.

Claims (4)

The viscosity at 25 ° C. after mixing containing 0.1 to 100 parts by weight of component (B) and 10 to 1000 parts by weight of component (C) is at least 0.1 parts by weight with respect to 100 parts by weight of component (A). A crosslinkable rubber composition characterized by having a pressure of 01 Pa · s to 10,000 Pa · s.
(A) having structural units derived from ethylene, an α-olefin having 3 to 20 carbon atoms, and at least one non-conjugated polyene represented by the following general formula [I] or [II], ) To (c) ethylene / α-olefin / non-conjugated polyene copolymer (a) The molar ratio of ethylene unit / α-olefin unit is 35/65 to 95/5.
(B) Iodine number is 0.5-50g / 100g
(C) Intrinsic viscosity [η] measured with a decalin solution at 135 ° C. is 0.01 to 5 dl / g
[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]
(B) Hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule (C) Nonpolar hydrocarbon oil The crosslinkable rubber composition according to claim 1, wherein the nonpolar hydrocarbon oil (C) has a dynamic viscosity of 40 ° C. and 1 to 10,000 mm ² / s.   The crosslinkable rubber composition according to claim 1 or 2, wherein the nonpolar hydrocarbon oil (C) is an ethylene / α-olefin copolymer.   A crosslinked rubber molded article obtained by crosslinking the crosslinkable rubber composition according to any one of claims 1 to 3.