JP2002037962A - Rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition having a rapid curing rate and capable of providing a cured product having improved weather resistance and excellent in mechanical strength while keeping various kinds of characteristics of an ethylene-α-olefin-nonconjugated polyene copolymer rubber, such as heat resistance and chemical resistance. SOLUTION: This rubber composition comprises (A) a silyl group-containing ethylene-α-olefin-nonconjugated polyene random copolymer rubber containing a hydrolyzable silyl group having a specific structure in the molecule, (B) an organic rubber and (C) a cross-linking agent for the organic rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to (A) a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber, (B) an organic rubber, and (C) a crosslinking agent for the organic rubber. It relates to a rubber composition.

[0002]

2. Description of the Related Art The main chain skeleton of an ethylene / α-olefin / non-conjugated polyene random copolymer rubber is composed of a structural unit derived from ethylene and a structural unit derived from an α-olefin, and the carbon-carbon required for crosslinking. In order to introduce an unsaturated bond, a small amount of a non-conjugated polyene monomer is copolymerized as a third component. As a result, they are used as vulcanizable elastomers in which the heat resistance and weather resistance of the vulcanized product are significantly improved as compared with diene elastomers such as natural rubber, polyisoprene, and polybutadiene.
However, although the amount of carbon-carbon unsaturated bonds is significantly lower than that of diene elastomers, the weatherability of the vulcanizate is still impaired because of the carbon-carbon unsaturated bonds for vulcanization.

Further, from the viewpoint of the vulcanization rate, since there are few carbon-carbon unsaturated bonds, the vulcanization rate is slow and there is a limit to speeding up the production line in the vulcanization step, which contributes to an increase in cost. I have.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a vulcanizate of ethylene / α-olefin / non-conjugated polyene copolymer rubber which can be rapidly used while utilizing various properties such as excellent heat resistance and chemical resistance. An object of the present invention is to provide a rubber composition capable of improving the weather resistance at the vulcanization rate and obtaining a cured product excellent in mechanical strength.

[0005]

The present invention is the following rubber composition. 1. (A) a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the following general formula (1) in the molecule:

Embedded image (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group,
It represents a hydrolyzable group selected from an aminooxy group, a thioalkoxy group, an amino group, a mercapto group and an alkenyloxy group, and m is an integer of 0, 1 or 2. A rubber composition comprising (B) an organic rubber and (C) a crosslinking agent for the organic rubber. 2. The silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber has the following general formula (2) or (3)

Embedded image (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R ¹
Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X is a hydride group, a halogen group , An alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group, an amino group, a mercapto group and a alkenyloxy group, wherein m is 0, 1 or And n is an integer of 0 to 10
Is an integer. 2. The rubber composition according to the above 1, which has at least one silyl group-containing unit represented by the formula: 3. The silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber has the following general formula (4) and / or (5)

Embedded image (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. , N is an integer of 0 to 10.) The ethylene / α-olefin / non-conjugated polyene random copolymer rubber having at least one type of norbornene compound having a terminal vinyl group as a non-conjugated polyene represented by the following general formula ( 6)

Embedded image (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group, Represents a hydrolyzable group selected from an amino group, a mercapto group and an alkenyloxy group, and m is an integer of 0, 1, or 2.) 3. The rubber composition as described in 1 or 2 above, wherein a SiH group of the silicon compound is added to the bond. 4. 4. The rubber composition according to any one of the above 1 to 3, wherein X is an alkoxyl group. 5. The organic rubber of the component (B) is a hydrolyzable silyl group-containing polypropylene glycol rubber, a hydrolyzable silyl group-containing polyisobutylene rubber, natural rubber, polyisoprene, polybutadiene, styrene-butadiene copolymer rubber, polychloroprene, Acrylic rubber, acrylonitrile / butadiene copolymer rubber, ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated polyene copolymer rubber, butyl rubber, urethane rubber, silicone rubber or a combination thereof. The rubber composition according to any one of the above. 6. The organic rubber (B) is a hydrolyzable silyl group-containing polypropylene glycol rubber, a hydrolyzable silyl group-containing polyisobutylene rubber, natural rubber, polybutadiene, polyisoprene, styrene / butadiene copolymer rubber, silicone rubber or 6. The rubber composition according to the above 5, which is a combination thereof. 7. The rubber composition according to the above item 5, wherein the organic rubber as the component (B) is an ethylene / propylene copolymer rubber, an ethylene / propylene / non-conjugated polyene copolymer rubber, a butyl rubber, an acrylic rubber, or a combination thereof. 8. (C) The crosslinking agent of the component is sulfur, sulfur donor,
Low sulfur high vulcanization accelerator, quinoid, peroxide, S
8. The rubber composition according to any one of the above 1 to 7, which is an i-group-containing compound or a resin. (D) The rubber composition according to any one of the above (1) to (8), which contains a silanol condensation catalyst as a component. 10. 10. The rubber composition according to the above item 9, wherein the silanol condensation catalyst as the component (D) is a tin compound. The above-mentioned 9 wherein the silanol condensation catalyst of the component (D) is an aluminum compound and / or a titanium compound.
11. The rubber composition described in 12. above. A crosslinked rubber elastic body obtained by crosslinking the rubber composition according to claim 1. 13. (A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula (1) and having substantially no unsaturated double bond in the main chain, (B) an organic rubber, and (C) A crosslinkable rubber composition containing the organic rubber crosslinking agent, which is used for electric / electronic parts, transportation equipment, civil engineering / architecture, medical care, or leisure. 14． Electric and electronic parts are used for heavy electric parts, light electric parts,
Sealing materials, potting materials, coating materials or adhesives for circuits and boards of electric and electronic equipment; repair materials for electric wire coatings; insulating sealing materials for electric wire joint parts; rolls for office automation equipment; vibration absorbers; or encapsulation of gels or capacitors 14. The rubber composition according to the above 13, which is a material. 15. 15. The rubber composition according to the above 14, wherein the sealing material is used as a sealing material for a refrigerator, a freezer, a washing machine, a gas meter, a microwave oven, a steam iron, or an earth leakage breaker. 16. 15. The potting material described in 14 above, wherein the potting material is used for potting a transformer high-voltage circuit, a printed circuit board, a high-voltage transformer with a variable resistor, an electrical insulating component, a semiconductive component, a conductive component, a solar cell or a flyback transformer for a television. Rubber composition. 17． The coating material is a high-voltage thick film resistor or a circuit element of a hybrid IC; HIC;
A conductive composition; a module; a printed circuit; a ceramic substrate; a buffer material for a diode, a transistor or a bonding wire; a semiconductive element; or a rubber composition according to the above 14, which is used for coating an optical fiber for optical communication. object. 18. 15. The rubber composition according to the above 14, wherein the adhesive is used for bonding a cathode ray tube wedge, a neck, an electrically insulating part, a semiconductive part or a conductive part. 19. 14. The crosslinkable rubber composition as described in 13 above, wherein the use of the transport machine is the use of an automobile, a ship, an aircraft, or a railway vehicle. 20. Automotive applications include automobile engine gaskets,
Sealing materials for electrical components or oil filters;
Botting material for igniter HIC or hybrid IC for automobile; coating material for automobile body, automobile window glass or engine control board;
20. The rubber composition according to 19 above, which is an adhesive for a gasket for an oil pan, a gasket for a timing belt cover, a molding, a headlamp lens, a sunroof seal, or a mirror. 21. 20. The rubber composition according to the above item 19, wherein the use of the ship is a wiring connection branch box, a sealing material for electric system parts or electric wires; or an adhesive for electric wires or glass. 22. Civil and architectural applications are jointing joints of glass screen method in commercial buildings, joints around glass between sashes, interior joints in toilets, washrooms or showcases, joints around bathtubs, outer joints for prefabricated houses. Sealants for building materials used for joints for sizing boards; Sealants for double glazing; Sealants for civil engineering used for road repair; Paints and adhesives for metals, glass, stone, slate, concrete or tile; 14. The rubber composition according to the above 13, which is used for a sheet, a waterproof sheet or a vibration-proof sheet. 23. 14. The rubber composition according to the above 13, wherein the medical use is a sealing material for a medical rubber stopper, a syringe gasket, or a rubber stopper for a reduced-pressure blood vessel. 24. 14. The rubber composition according to the above 13, wherein the leisure use is a swimming member for a swimming cap, a diving mask or earplugs; or a gel cushioning member for sports shoes or baseball gloves. 25. (A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula (1) and having substantially no unsaturated double bond in the main chain, (B) an organic rubber, and (C) A sealing material comprising a crosslinkable rubber composition containing the organic rubber crosslinking agent. 26. (A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula (1) and having substantially no unsaturated double bond in the main chain, (B) an organic rubber, and (C) A potting material comprising a crosslinkable rubber composition containing the organic rubber crosslinking agent. 27. (A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula (1) and having substantially no unsaturated double bond in the main chain, (B) an organic rubber, and (C) A coating material comprising a crosslinkable rubber composition containing the organic rubber crosslinking agent. 28. (A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula (1) and having substantially no unsaturated double bond in the main chain, (B) an organic rubber, and (C) An adhesive comprising a crosslinkable rubber composition containing the organic rubber crosslinking agent.

Hereinafter, the present invention will be described in more detail. The silyl group-containing silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (hereinafter sometimes also referred to as “silyl group-containing copolymer rubber”) as the component (A) is represented by the above general formula (1) a structural unit derived from a non-conjugated polyene having a hydrolyzable silyl group, preferably containing at least one terminal vinyl group represented by the above general formula (4) or (5) Ethylene / α-olefin / norbornene compound
The non-conjugated polyene random copolymer rubber contains a silyl group represented by the above general formula (1) on the side chain or terminal.

In the general formula (1), R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably one having no aliphatic unsaturated bond, for example, methyl, ethyl , An alkyl group such as propyl, butyl, hexyl, cyclohexyl, an aryl group such as phenyl and tolyl, and a group obtained by substituting part or all of the hydrogen atoms bonded to these carbon atoms with a halogen atom such as a fluorine atom. No. X is a hydride group, a halogen group,
Alkoxyl group, acyloxy group, ketoxime group,
And a group selected from an amide group, an acid amide group, an aminooxy group, a thioalkoxy group, an amino group, a mercapto group and an alkenyloxy group. Among these, an alkoxyl group, particularly an alkoxyl group having 1 to 4 carbon atoms, is preferred. m
Is an integer of 0, 1 or 2, preferably 0 or 1.
It is. In addition, R, X, and m in the general formulas (2), (3), and (6) are the same as above.

The number of silyl groups in one molecule of the silyl group-containing copolymer rubber is one or more, and the average of the number is 0.1 to 10
It is preferred that there are. If the number of silyl groups contained in the molecule is less than 0.1, the curability becomes insufficient and good rubber elasticity may not be obtained.

The method for producing the silyl group-modified ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group of the present invention is not particularly limited. (4)
Or a hydrosilylation reaction of a silicon compound represented by the general formula (6) with an ethylene / α-olefin / non-conjugated polyene random copolymer rubber comprising at least one type of norbornene compound having a terminal vinyl group represented by the formula (5) Is preferred.

The ethylene / α-olefin / non-conjugated polyene random copolymer rubber which is reacted with the silicon compound represented by the general formula (6) is composed of ethylene, α-olefin having 3 to 20 carbon atoms, It is a random copolymer with a conjugated polyene. 3 to 20 carbon atoms
As the α-olefin, specifically, propylene,
1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 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 them, 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 preferably used in the present invention is a norbornene compound having a terminal vinyl group represented by the general formula (4) or (5). General formula (4)
In the above, n is an integer of 0 to 10. R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
^As an alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group,
t-butyl group, n-pentyl group, isopentyl group, t-
Examples include a pentyl group, a neopentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. R ² is a hydrogen atom or a carbon atom having 1 to 1
5 alkyl groups. Specific examples of the alkyl group having 1 to 5 carbon atoms of R ² include the alkyl groups having 1 to 5 carbon atoms among the specific examples of the above R ¹ . In the general formula (5), R ³ represents a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl groups. Specific examples of the alkyl group of R ³ include the same alkyl groups as the specific examples of the alkyl group of R ¹ . Incidentally, R ^1, n in the general formula (2) is the same as R ^1, n in the general formula (4), R ³ in the general formula (3) is the general formula (5)
And R ³ is the same as described above.

As the norbornene compound represented by the general formula (4) or (5), 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-hexyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2- Norbornene and the like. Among them, 5-vinyl-2-norbornene, 5-methylene-2
-Norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene,
-(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.

In addition to the above norbornene compounds such as 5-vinyl-2-norbornene, the following non-conjugated polyenes can be used in combination as long as the physical properties aimed at by the present invention are not impaired. Specific examples of such a non-conjugated polyene include 1,4-hexadiene and 3-methyl-
Chains such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, and 7-methyl-1,6-octadiene Non-conjugated diene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-
Cyclic unconjugated dienes such as chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene;
3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2
And trienes such as -propenyl-2,2-norbornadiene.

[0014] Ethylene / α comprising the above components
-The olefin / non-conjugated polyene random copolymer has the following composition. (I) Molar ratio of ethylene to α-olefin having 3 to 20 carbon atoms (ethylene / α-olefin) Ethylene / α-olefin / non-conjugated polyene random copolymer rubber is a unit derived from (a) ethylene And (b)
A unit derived from an α-olefin having 3 to 20 carbon atoms (hereinafter, sometimes simply referred to as α-olefin);
0/60 to 95/5, preferably 50/50 to 90/1
0, more preferably 55 / 45-85 / 15, particularly preferably 60 / 40-80 / 20 [(a) /
(B)]. When this molar ratio is within the above range, a rubber composition which is excellent in heat aging resistance, strength properties and rubber elasticity and can provide a vulcanized rubber molded article excellent in cold resistance and processability is obtained.

(Ii) Iodine value The iodine value of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber is 0.5 to 50 (g / 100).
g), preferably 0.8 to 40 (g / 100 g), more preferably 1 to 30 (g / 100 g), particularly preferably 1.5 to 25 (g / 100 g). Here, the iodine value is a value corresponding to the amount of double bonds contained in the structural unit derived from norbornene having a terminal vinyl group represented by the above general formula (4) and / or general formula (5). When the iodine value is within the above range, the vulcanizable rubber can be adjusted to a desired content of the hydrolyzable silyl group, and is excellent in compression set resistance and environmental deterioration resistance (heat aging resistance). A rubber composition that can provide a molded article is obtained. If the iodine value exceeds 50, it is disadvantageous in terms of cost, which is not preferable. (Iii) Intrinsic Viscosity The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber measured at 135 ° C. in decalin is 0.001 to 2 dl / g, preferably 0.0
1-2 dl / g, more preferably 0.05-1 dl / g
g, particularly preferably 0.05 to 0.7 dl / g, most preferably 0.1 to 0.5 dl / g. When the intrinsic viscosity [η] is within the above range, a rubber composition having excellent fluidity and capable of providing a crosslinked rubber molded article having excellent strength properties and compression set resistance can be obtained.

(Iv) Molecular weight distribution (Mw / Mn) Molecular weight distribution (Mw / Mn) of ethylene / α-olefin / non-conjugated polyene random copolymer rubber measured by GPC
Mn) is 3 to 100, preferably 3.3 to 75, and more preferably 3.5 to 50. This molecular weight distribution (M
When (w / Mn) is within the above range, a rubber composition which is excellent in processability and can provide a crosslinked rubber molded article having excellent strength properties is obtained.

The ethylene / α-olefin / non-conjugated polyene random copolymer rubber has a polymerization temperature of 30 to 60 ° C., particularly 30 to 60 ° C., in the presence of a catalyst containing the following compounds (H) and (I) as main components. 59 ° C, polymerization pressure 4-12
kgf / cm ^2, particularly 5~8kgf / cm ^2, the supply amount molar ratio of the non-conjugated polyene and ethylene (non-conjugated polyene /
Ethylene) Under conditions of 0.01 to 0.2, ethylene, an α-olefin having 3 to 20 carbon atoms and a norbornene compound having a terminal vinyl group represented by the above general formula (4) or (5) are randomly selected. It is obtained by copolymerization. The copolymerization is preferably carried out in a hydrocarbon medium.

(H) 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 1-3. A vanadium compound 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 a hydrocarbon medium of a polymerization reaction system, and specifically, has the general formula VO (OR) _{a Xb} or V (OR) _c X _d (where R Is a hydrocarbon group, and 0 ≦ a
≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦
Vanadium compounds represented by d ≦ 4, 3 ≦ c + d ≦ 4) or their electron donor adducts can be mentioned as typical examples. More specifically, VOCl ₃ , V
O (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₆ ) ₂ Cl, VO
_{(O-iso-C 3 H} 7) Cl 2, VO (O-n-C 4 H 9) C
l ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₃ , VCl ₄ , VOC
_{l 3, VO (O-n} -C 4 H 9) 3, VCl 3 · 2OC 6 H 12
OH and the like can be exemplified.

(I) An organoaluminum compound represented by R ' _m AlX' _3-m (R 'is a hydrocarbon group, X' is a halogen atom, and m is 1 to 3). Specific examples of the organoaluminum compound (I) include trialkylaluminums such as triethylaluminum, tributylaluminum, and triisopropylaluminum;
Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially having an average composition represented by R _0.5 Al (OR ¹ ) _0.5 Alkoxylated alkylaluminum; diethylaluminum chloride,
Dialkylaluminum halides such as dibutylaluminum chloride and diethylaluminum bromide; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide, alkylaluminums such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide Partially halogenated alkyl aluminum such as dihalide; partially hydrogenated alkyl aluminum dihydride such as diethyl aluminum hydride, dialkyl aluminum hydride such as dibutyl aluminum hydride, ethyl aluminum dihydride and propyl aluminum dihydride; Alkyl aluminum; ethyl aluminum Kishikurorido, butylaluminum butoxide cycloalkyl chloride, etc. partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide and the like.

Of the above compound (H), a soluble vanadium compound represented by VOCl ₃ and the above compound (I)
Of these, Al (OC ₂ H ₅ ) ₂ Cl / Al ₂ (OC ₂ H ₅ ) ₃
When a blend of Cl 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 ・
It is preferable because a non-conjugated polyene random copolymer rubber can be obtained. Further, as a catalyst used in the above copolymerization,
So-called metallocene catalysts, for example,
May be used.

Next, the above-mentioned ethylene / α-olefin / non-conjugated polyene random copolymer rubber is subjected to a hydrosilylation reaction (hydrosilylation reaction) with a silicon compound represented by the above general formula (6) to give a silyl group-modified ethylene. A method for producing an α-olefin / non-conjugated polyene copolymer rubber will be described.

Examples of the hydrolyzable group represented by X in the general formula (6) will be described. A hydride group is a hydrogen atom. Examples of the halogen group include a chlorine atom,
Examples include a fluorine atom, a bromine atom and an iodine atom. Examples of the alkoxyl group include a methoxy group, an ethoxy group,
Propoxy group, propoxybutoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, tert-
Butoxy, pentyloxy, hexyloxy, phenoxy and the like. As the acyloxy group,
Examples include an acetoxy group and a benzoyloxy group. Ketoximate groups include acetoximate groups,
Examples thereof include a dimethyl keto xymate group, a diethyl keto oximate group, and a cyclohexyl keto oximate group.
Examples of the amide group include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, and a diphenylamide group. Examples of the acid amide group include a carboxylic acid amide group, a maleic acid amide group, an acrylic acid amide group, and an itaconic acid amide group. Examples of the thioalkoxy group include thiomethoxy, thioethoxy, thiopropoxy, thioisopropoxy, sec
-Thiobutoxy group, tert-thiobutoxy group, thiopentyloxy group, thiohexyloxy group, thiophenoxy group and the like. Examples of the amino group include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diphenylamino group, and the like. Among these, an alkoxyl group is preferred.

Specific examples of the silicon compound represented by the general formula (6) include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane,
Halogenated silanes such as diethylchlorosilane, phenyldichlorosilane and diphenylchlorosilane; trimethoxysilane, triethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, butyldimethoxysilane, methyldiethoxysilane, ethyldiethoxysilane, butylethoxysilane, Alkoxysilanes such as phenyldimethoxysilane; acyloxysilanes such as triacetoxysilane, methyldiacetoxysilane and phenyldiacetoxysilane; tris (acetoxymate) silane and bis (dimethylketoxime) methylsilane;
Examples include ketoxime silanes such as bis (methylethylketoxime) methylsilane and bis (cyclohexylketoxime) methylsilane; and aminooxysilanes such as aminooxysilane and triaminooxysilane. Of these, alkoxysilanes are particularly desirable.

The amount of the silicon compound of the above general formula (6) to be used is from 0.01 to 0.01 per mole of double bond in the ethylene / α-olefin / non-conjugated polyene random copolymer rubber which reacts with the silicon compound. 5 moles, preferably 0.05-3
It is preferred to be molar.

The reaction is preferably carried out using a transition metal complex catalyst. As the catalyst, for example, a Group VIII transition metal complex compound selected from platinum, rhodium, cobalt, palladium and nickel is effectively used. Of these, platinum-based catalysts such as chloroplatinic acid and platinum-olefin complexes are particularly preferred. In this case, the amount of the catalyst used is a catalytic amount, but is preferably 0.1 to 10000 ppm as a metal unit with respect to the reactant, more preferably 1 to 1 ppm.
000 ppm, particularly preferably 20 to 200 ppm. The preferred temperature for this hydrosilation reaction is 3
The temperature is 0 to 180 ° C, preferably 60 to 150 ° C. Moreover, you may make it react under pressure as needed. The reaction time is about 10 seconds to 10 hours.

The solvent may or may not be used, but when used, an inert solvent such as ethers and hydrocarbons is preferred.

By the above hydrosilylation reaction,
The SiH group of the silicon compound represented by the general formula (6) is added to the double bond derived from the non-conjugated polyene in the ethylene / α-olefin / non-conjugated polyene random copolymer rubber. In the case of the formula (4) or (5), a silyl group-containing unit represented by the general formula (2) or (3) is generated.

At the time of the reaction, a one-terminal hydrogen-modified siloxane represented by the following formula (7) is added together with the silicon compound represented by the above-mentioned general formula (6) to obtain weather resistance, slipperiness, and gas characteristics characteristic of the siloxane. It is also possible to impart transparency.

[0029]

Embedded image

(In the formula, R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, particularly preferably an alkyl group, and p is 5 to 200, particularly preferably It is an integer of 10 to 150.)

In the rubber composition of the present invention, the content of the silyl group-containing copolymer rubber is preferably at least 10%, more preferably at least 20%, particularly preferably at least 30%.

The organic rubber as the component (B) contained in the rubber composition of the present invention includes hydrolyzable silyl group-containing polypropylene glycol rubber, hydrolyzable silyl group-containing polyisobutylene rubber, natural rubber, and polyisoprene. , Polybutadiene, styrene / butadiene copolymer rubber, polychloroprene, acrylic rubber, acrylonitrile / butadiene copolymer rubber, ethylene / propylene copolymer rubber (EPM), ethylene / propylene / non-conjugated polyene copolymer rubber (EPDM) Butyl rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, ethylene / vinyl acetate copolymer rubber, ethylene / acrylic copolymer rubber, fluorine rubber, chlorosulfonated polyethylene, and combinations thereof.

Of these, when considering compatibility with the component (A), in particular, hydrolyzable silyl group-containing polypropylene glycol rubber, hydrolyzable silyl group-containing polyisobutylene rubber, natural rubber, polyisoprene, polybutadiene Styrene / butadiene copolymer rubber, polychloroprene, acrylic rubber, acrylonitrile / butadiene copolymer rubber, ethylene / propylene copolymer rubber (EPM), ethylene / propylene / non-conjugated polyene copolymer rubber (EPDM), butyl rubber , Urethane rubber,
Preferred are ethylene / acrylic copolymer rubbers, silicone rubbers and combinations thereof. However, when a compatibilizer is used, other than these rubbers can be preferably used.

The proportion of the silyl group-containing copolymer rubber of the component (A) and the organic rubber of the component (B) is 3% of that of the component (A).
From the viewpoint of forming a three-dimensional crosslinked structure, workability, and mechanical strength, the weight ratio ((A) / (B)) is usually 3%.
/ 97 to 70/30, preferably 5/95 to 50
/ 50 range.

The component (C) used in the present invention is usually
There is no particular limitation on the rubber vulcanizing agent as long as it can be used for EPDM. Examples include sulfur, sulfur donors, low sulfur and high vulcanization accelerators, quinoids, resins, peroxides, SiH group compounds, and the like. In addition, as the component (C) of the present invention, a polyfunctional crosslinking agent having two or more functional groups having reactivity with a crosslinking group contained in the organic rubber (B) can be mentioned. Examples of the functional group include an amino group, an isocyanate group, a maleimide group, an epoxy group, a hydrosilyl group, and a carboxyl group.

The rubber composition of the present invention may contain a curing catalyst for promoting a silanol condensation reaction. As such a curing catalyst, conventionally known curing catalysts can be widely used. Specific examples thereof include titanates such as tetrabutyl titanate and tetrapropyl titanate; tin carboxylate salts such as cibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate; and cibutyltin oxide. Reaction product with phthalic acid ester; Cybutyltin diacetylacetonate; Organic aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisoproposhialuminum ethylacetoacetate; zirconium tetraacetylacetonate, titanium tetraacetyl Chelating compounds such as acetonate; lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine Emissions, triethanolamine,
Diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine,
Diethylaminopropylamine, xylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo [5.4.0] Amine compounds such as undecene-7 (DBU) or salts thereof with carboxylic acids and the like; low molecular weight polyamide resins obtained from excess polyamine and polybasic acid; excess polyamine and epoxy Reaction product with a compound; a silane coupling agent having an amino group, for example, γ
Examples thereof include silanol condensation catalysts such as -aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane, and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts. These catalysts may be used alone or in combination of two or more.

When a curing catalyst is used, its compounding amount is
The amount is usually about 0.1 to 20 parts by weight, preferably about 1 to 10 parts by weight, per 100 parts by weight of the component (A). If the amount of the curing catalyst relative to the component (A) is too small, the curing rate of the obtained rubber composition will be low. On the other hand, if it is too large, the physical properties such as tensile properties of the obtained cured product will be reduced. Absent.

The rubber composition of the present invention further comprises an adhesion improver, a physical property modifier, a storage stability improver, a plasticizer, an antioxidant, an ultraviolet absorber, a metal deactivator, an ozone deterioration inhibitor, Various additives such as a light stabilizer, an amine-based radical chain inhibitor, a phosphorus-based peroxide decomposer, a lubricant, a pigment, and a foaming agent can be appropriately added.

Here, as the adhesiveness improving agent, generally used adhesives and other compounds other than the silane coupling agent as the component (D) can be used. Specific examples of such an adhesion improver include a phenol resin, an epoxy resin, a coumarone-indene resin,
Rosin ester resin, terpene-phenol resin, α-
Examples thereof include a methylstyrene-vinyltoluene copolymer, polyethylmethylstyrene, alkyl titanates, and aromatic polyisocyanates. When the adhesion improver is blended, the amount is preferably about 1 to 50 parts by weight, more preferably about 5 to 30 parts by weight, per 100 parts by weight of the component (A).

Examples of the storage stability improver include compounds in which a hydrolyzable group is bonded to a silicon atom, and ortho organic acid esters. Specific examples of such storage stability improvers include methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, dimethyldiethoxysilane, trimethylisobutoxysilane, and trimethyl (n-butoxy) silane. , N-butyltrimethoxysilane and methyl orthoformate. When the storage stability improver is compounded, the compounding amount is preferably about 0.5 to 2 parts by weight, more preferably about 1 to 10 parts by weight, per 100 parts by weight of (A).

The plasticizer is not particularly limited, and any commonly used plasticizer can be used, but a plasticizer having good compatibility with various components to be blended in the rubber composition of the present invention is preferable. Specific examples of such a plasticizer include, for example, polybutene, hydrogenated polybutene, ethylene / α-olefin oligomer, α-methylstyrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylenetriphenyl, liquid polybutadiene, hydrogenated Hydrocarbon compounds such as liquid polybutadiene, alkyl diphenyl, partially hydrogenated terphenyl, paraffin oil, naphthenic oil, atactic polypropylene; paraffin chlorides; dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl Phthalates such as phthalate and butylphthalylbutyl glycolate; non-aromatic dibasic esters such as dioctyl adipate and dioctyl sebacate; diethylene glycol benzoate, triethylene Esters of polyalkylene glycol such as glycol dibenzoate; phosphates such as tricresyl phosphate and tributyl phosphate; These may be used alone or in combination of two or more. Among these, hydrocarbon compounds having no unsaturated group (specifically, hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, atactic polypropylene, etc.)
Good compatibility with various components to be blended in the composition of the present invention, less influence on the curing rate of the rubber composition, and good weatherability of the obtained cured product, and inexpensive, preferred .

When introducing a reactive silicon group into the ethylene / α-olefin / non-conjugated polyene copolymer rubber, these plasticizers are used to adjust the reaction temperature and the viscosity of the reaction system. It may be used instead.

When the plasticizer is compounded, the compounding amount is
The amount is preferably about 10 to 500 parts by weight, more preferably about 20 to 300 parts by weight, per 100 parts by weight of the component (A).

Specific examples of the above-mentioned filler include, for example, wood flour, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice hull powder, graphite, diatomaceous earth, terra alba, fume silica, sedimentation Silica, silica, carbon black, calcium carbonate, clay,
Examples include talc, titanium oxide, magnesium carbonate, quartz, aluminum fine powder, flint powder, zinc powder and the like.
Among these fillers, fillers having thixotropic properties, such as precipitated silica, fumed silica, and carbon black, calcium carbonate, titanium oxide, and talc are preferable. When the filler is blended, the blending amount is (A)
10 parts per 100 parts by weight of the total amount of the component and the component (B)
It is preferably about 500 parts by weight, more preferably about 20 to 300 parts by weight.

Examples of the antioxidant include well-known antioxidants which are generally used, for example, sulfur-based antioxidants, radical inhibitors, ultraviolet absorbers and the like. Examples of the sulfur-based antioxidants include mercaptans, salts of mercaptans, sulfides including sulfide carboxylate esters and hindered phenol sulfides, polysulfides, dithiocarboxylates, thioureas, thiophosphates, sulfonium Examples include compounds, thioaldehydes, thioketones, mercaptals, mercaptols, monothio acids, polythio acids, thioamides, sulfoxides and the like. Specific examples of the sulfur-based antioxidant include 2-mercaptobenzothiazole which is a mercaptan, zinc salt of 2-mercaptobenzothiazole which is a salt of mercaptan, and sulfides which are 4,4.
4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-thio-bis (2-methyl-6-t-butylphenol), 2,2'-thio-bis (4-methyl −
6-t-butylphenol), bis (3-methyl-4-)
(Hydroxy-5-t-butylbenzyl) sulfide, terephthaloyldi (2,6-dimethyl-4-t-butyl-
3-hydroxybenzyl) sulfide, phenothiazine, 2,2'-thio-bis (4-octylphenol) nickel, dilaurylthiodipropionate, distearylthiodipropionate, dimyristylthiodipropionate, ditridecylthiodipropionate , Distearyl β, β'-thiodibutyrate, lauryl-stearylthiodipropionate, 2,2-thio [diethyl-bis-3- (3,5-di-t-butyl-4-hydroxyphenol) propionate ], 2-benzothiazole disulfide which is a polysulfide, tinc dibutyl dithiocarbamate which is a dithiocarboxylate, tinc diethyldithiocarbamate, nickel dibutyldithiocarbamate, tincdi-n-butyldithiocarbamate, dibutylammonium Butyl dithiocarbamate, Chinkuechiru - phenyl - dithiocarbamate, Tink dimethyl geo carbamate is thioureas 1
-Butyl-3-oxy-diethylene-2-thiourea,
Examples thereof include di-o-tolyl-thiourea, ethylene thiourea, and trilauryl trithiophosphate, which is a thiophosphite. When such a sulfur-based antioxidant is used in the rubber composition of the present invention as compared with other antioxidants, it can significantly prevent degradation of the main chain due to heat, and has a surface tack (stickiness). ) Can be prevented.

As the radical inhibitor, for example, 2,
2-methylene-bis (4-methyl-6-t-butylphenol), tetrakis [methylene-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] a phenolic radical inhibitor such as methane, phenyl-β-naphthylamine, α-naphthylamine, N, N ′
And amine-based radical inhibitors such as -sec-butyl-p-phenylenediamine, phenothiazine, and N, N'-diphenyl-p-phenylenediamine. Examples of the ultraviolet absorber include 2- (2′-hydroxy-
3 ', 5'-di-t-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and the like. When the antioxidant is incorporated, the amount is preferably about 0.1 to 20 parts by weight, more preferably about 1 to 10 parts by weight, per 100 parts by weight of the component (A).

The rubber composition of the present invention is prepared by uniformly kneading the above components using a kneading machine such as an intermix mixer, a planetary mixer, a Banbury mixer, a kneader, or a two-roll mill. be able to. Further, the curing of the rubber composition of the present invention is performed at room temperature to 200 ° C. for several minutes to several days because the curing rate is high. In particular, it is preferable to crosslink by reacting with moisture in the air.

(Use of Rubber Composition) The rubber composition of the present invention includes a rubber composition containing a hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber as the component (A). The organic polymer containing a hydrolyzable silyl group represented by the general formula (1) and having substantially no unsaturated bond in the main chain is used for electric / electronic parts, transportation equipment, civil engineering / architecture, Used for medical or leisure purposes.

Specific examples of the use of electric / electronic parts include heavy electric parts, light electric parts, sealing materials, potting materials, coating materials or adhesive materials for circuits and boards of electric / electronic devices; repair materials for electric wire coatings. An insulating seal material for electric wire joint parts; a roll for OA equipment; a vibration absorber; or an encapsulating material for gel or a capacitor.

The above sealing material is suitably used as a sealing material for, for example, refrigerators, freezers, washing machines, gas meters, microwave ovens, steam irons, and earth leakage breakers.

The above-mentioned potting material is suitable for potting, for example, a transformer high-voltage circuit, a printed circuit board, a high-voltage transformer with a variable resistor, an electrical insulating component, a semiconductive component, a conductive component, a solar cell or a flyback transformer for a television. Used for

The coating material may be, for example, various circuit elements such as high voltage thick film resistors or hybrid ICs; HICs, electrically insulating parts; semiconductive parts; conductive parts; modules; printed circuits; It is suitably used for coating a buffer material such as a bonding wire; a semiconductive element; or an optical fiber for optical communication.

The above-mentioned adhesive is suitably used for bonding cathode ray tube wedges, necks, electrically insulating parts, semiconductive parts or conductive parts, for example. Examples of the use of the transport machine include a car, a ship, an aircraft, and a railway vehicle.

Examples of the use of an automobile include a sealing material for a gasket, an electric component or an oil filter of an automobile engine; a botting material for an igniter HIC or an automobile hybrid IC; a coating material for an automobile body, an automobile window glass, and an engine control board. Or gaskets such as oil pans or timing belt covers, moldings, headlamp lenses, sunroof seals, adhesives for mirrors, and the like.

Examples of the use of a ship include a wiring junction box, a sealing material for electric system parts or electric wires, and an adhesive for electric wires or glass. Examples of the use of the civil engineering construction include, for example, a joint joint of a glass screen method in a commercial building, a joint around a glass between a sash, an interior joint in a toilet, a washroom or a showcase, a joint around a bathtub, and a prefabricated house. Sealants for building materials used for expansion joints and sizing board joints; Sealants for double glazing; Sealants for civil engineering used to repair roads; Paints and adhesives for metals, glass, stone, slate, concrete or tile And an adhesive sheet, a waterproof sheet or a vibration-proof sheet.

The above medical uses include, for example, rubber stoppers for pharmaceuticals, syringe gaskets, rubber stoppers for reduced-pressure blood vessels, and the like. Examples of the leisure use include swimming members such as swimming caps, diving masks, and ear plugs; and gel buffer members such as sports shoes and baseball gloves.

The rubber composition of the present invention can be used for electric / electronic parts,
It can be suitably used as a sealing material (sealing material), a potting material, a coating material, and an adhesive in applications such as transportation, civil engineering, and leisure.

[0058]

EFFECT OF THE INVENTION The rubber composition of the present invention comprises (A) a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer containing a hydrolyzable silyl group represented by the above general formula (1) in the molecule. Since it contains a polymer rubber, (B) an organic rubber, and (C) a crosslinking agent for the organic rubber, the vulcanization rate is high, and the cured rubber elastic body obtained by vulcanization has excellent weather resistance, heat resistance, It has chemical resistance, etc., and is also excellent in mechanical strength. Therefore, hoses, anti-vibration materials, belts, coupling materials, weatherstrip materials, glass channels, electric wires, condenser seal rubber, waterproof sheets, sealants, adhesives, sealing applications for double-glazing, applications as molding materials for shoe soles, etc. It is particularly suitable for

[0059]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in detail with reference to examples, but the present invention is not limited to the examples.

(Production Example 1) [Silyl group-containing ethylene / propylene / 5-vinyl-2]
-Production of norbornene random copolymer rubber] Ethylene, propylene and 5-vinyl-2-norbornene are continuously used using a stainless steel polymerization vessel (stirring rotation speed = 250 rpm) equipped with a stirring blade and having a substantial internal volume of 100 liters. Was terpolymerized. 60 liters of hexane, 2.5 kg of ethylene, 4.0 kg of propylene, and 3 parts of 5-vinyl-2-norbornene per hour were added to the liquid phase from the side of the polymerization vessel.
At a rate of 80 g, 700 liters of hydrogen, 45 mmol of VO (OC ₂ H ₅ ) ₂ Cl as a catalyst, Al (E
t) _1.5 Cl _1.5 was fed continuously at a rate of 315 mmol. When the copolymerization reaction was carried out under the conditions described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber was obtained in a uniform solution state. Thereafter, a small amount of methanol was added to the polymerization solution continuously withdrawn from the lower part of the polymerization vessel to stop the polymerization reaction, and the polymer was separated from the solvent by steam stripping, followed by vacuum drying at 55 ° C. for 48 hours. Was done. The ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber obtained as described above has an ethylene content of 68 mol%, an iodine value of 10, and an intrinsic viscosity [η].
0.2 dl / g and molecular weight distribution (Mw / Mn) were 15.

2% for 100 g of the produced ethylene / propylene / 5-vinyl-2-norbornene copolymer rubber
0.3 g of a toluene solution of chloroplatinic acid was added, 1.5 g of methyldimethoxysilane was charged, and reacted at 120 ° C. for 2 hours. After the reaction, excess methyldimethoxysilane and the solvent were distilled off to obtain 101.5 g of a dimethoxymethylsilyl group-containing copolymer rubber.

Examples 1 to 5 According to the formulation shown in Table 1, the dimethoxysilyl group-containing copolymer rubber produced in the above production example was used as the component (A), and polybutadiene was used as the organic rubber of the component (B). Rubber, styrene-butadiene copolymer rubber, acrylic rubber (AR101 made by Nippon Synthetic Rubber), hydrolyzable silyl group-containing polypropylene glycol (Kanebuchi Chemical Co., Ltd.)
, MS Polymer, MS203, trade name), nitrile rubber (N230S, manufactured by Nippon Synthetic Rubber Co., Ltd.) and 120 using Banbury mixer (manufactured by Kobe Steel, 1.9).
A vulcanizing agent and the like were further added at 5 ° C. for 5 minutes with an 8-inch open roll and kneaded to obtain respective rubber compositions (compounded rubber). Comply with this sample JISK6300-1994, was measured vulcanization rate T _90. These were extruded into a sheet by a biaxial extruder, and continuously vulcanized (180 ° C. × 1 hour) to obtain a vulcanized sheet. The tensile test, heat resistance, surface weather resistance, curing speed, and weather resistance of the cured sheet were evaluated by the following methods. The results are shown in Table 1 below.

(Evaluation method) Tensile test In accordance with JIS 6251, a tensile test was performed at 23 ° C. using a JIS No. 1 dumbbell.

Weather resistance: Accelerated weather test: JIS B 7753 compliant Sunshine carbon arc weatherometer Irradiation / rain cycle: 120 minutes irradiation / 18 minutes rain Black panel temperature: 63 ± 2 ° C. In-bath temperature: 40 ± 2 C. Irradiation time: The surface state after 500 hours was observed. (Evaluation) ○: No crack dissolving portion △: Slight crack or slight dissolving portion ×: Crack or dissolving portion

Reference Examples 1 to 5 As shown in Table 1, in place of the silyl group-containing copolymer rubber as the component (A) in Examples,
The following compound A (number average molecular weight 10,600, molecular weight distribution (Mw / Mn) 1.2, terminal dimethoxymethylsilyl functional group 1.9) synthesized by the synthesis method described in Japanese Patent No. 105005, and others were used. Was carried out in the same manner as in the example, to obtain a sheet-like vulcanized rubber, which was evaluated. The results are shown in Table 1.

[0066]

Embedded image

[0067]

[Table 1]

From the results shown in Table 1, all of the rubber compositions of the examples were superior to the composition of the comparative example in curing speed, surface weather resistance of the cured product, weather resistance and heat resistance. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/057 C08K 5/057 4J100 5/08 5/08 4M109 5/14 5/14 5/36 5 / 36 5/541 5/56 5/56 5/57 5/57 C08L 21/00 C08L 21/00 C09D 121/00 C09D 121/00 123/26 123/26 183/04 183/04 C09J 121/00 C09J 121 / 00 123/26 123/26 183/04 183/04 C09K 3/00 PC09K 3/00 3/10 Z 3/10 G JD F16J 15/10 Y F16J 15/10 C08K 5/54 H01L 23/29 H01L 23/30 R 23/31 (72) Inventor Yoshiharu Kikuchi 3 Chizukaigan, Ichihara-shi, Chiba F-term (reference) in Mitsui Chemicals, Inc. 3J040 EA16 FA06 HA06 HA07 HA30 4H017 AA03 AB01 AB03 AB07 AB15 AC05 AD03 AD05 AD06 AE03 AE05 4J002 AC01X AC03X AC06X AC07X AC08X AC09X BB06X BB07X BB15 X BB18X BB20W BB20X BB27X BD12X BG04X CH04X CH05X CK02X CP03X CP17W DA046 EC077 EG047 EJ047 EK006 EK056 EN027 EN037 EN067 EN107 ER027 EU117 EU237 EV006 EX006 EX077 EZ007 EZ047 FD010 FD020 FD030 FD146 FD156 GC00 GH01 GJ01 GJ02 GL00 GN00 GQ00 GR00 4J038 CA011 CA012 CA041 CA042 CA071 CA072 CA081 CA082 CB101 CB102 CB131 CB132 CB141 CB142 CG141 CG142 DB002 DF021 DF022 DF041 DF042 DG001 DG002 DL031 DL032 FA182 GA15 HA046 JA23 JA34 JA47 JA66 JB01 CA01 CA2 CA09 CA01 CA03 CA08 CA152 DA121 DA122 DA141 DA142 DA151 DA152 DF041 DF042 EC002 EE021 EE022 EE051 EE052 EF001 EF002 EK031 EK032 FA192 GA31 HA046 HA096 HB07 HB21 HB24 HB41 BA01 CA01 A16A03 A CA31 DA04 DA09 DA31 HA35 HA61 HC79 JA01 JA03 JA05 JA28 JA43 JA44 JA50 JA57 JA67 4M109 BA01 BA03 CA04 CA10

Claims (28)

[Claims] 1. A (A) silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group represented by the following general formula (1) in the molecule: (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group,
It represents a hydrolyzable group selected from an aminooxy group, a thioalkoxy group, an amino group, a mercapto group and an alkenyloxy group, and m is an integer of 0, 1 or 2. A rubber composition comprising (B) an organic rubber and (C) a crosslinking agent for the organic rubber. 2. A silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber represented by the following general formula (2) or (3): (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, R ¹
Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X is a hydride group, a halogen group , An alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group, an amino group, a mercapto group and a alkenyloxy group, wherein m is 0, 1 or And n is an integer of 0 to 10
Is an integer. The rubber composition according to claim 1, which has at least one silyl group-containing unit represented by the formula: 3. The ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a silyl group is represented by the following general formula (4) and / or (5): (Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. , N is an integer of 0 to 10.) The ethylene / α-olefin / non-conjugated polyene random copolymer rubber having at least one type of norbornene compound having a terminal vinyl group as a non-conjugated polyene represented by the following general formula ( 6) (Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group, Represents a hydrolyzable group selected from an amino group, a mercapto group and an alkenyloxy group, and m is an integer of 0, 1, or 2.) The rubber composition according to claim 1, wherein the bond is obtained by adding a SiH group of the silicon compound to the bond. 4. The method according to claim 1, wherein X is an alkoxyl group.
The rubber composition according to any one of the above. 5. The organic rubber as the component (B) is a hydrolyzable silyl group-containing polypropylene glycol rubber, a hydrolyzable silyl group-containing polyisobutylene rubber, natural rubber, polyisoprene, polybutadiene, styrene / butadiene copolymer. Rubber, polychloroprene, acrylic rubber, acrylonitrile / butadiene copolymer rubber, ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated polyene copolymer rubber, butyl rubber, urethane rubber, silicone rubber or a combination thereof Item 1
5. The rubber composition according to any one of items 1 to 4. 6. The organic rubber as the component (B) is a hydrolyzable silyl group-containing polypropylene glycol rubber, a hydrolyzable silyl group-containing polyisobutylene rubber, natural rubber, polybutadiene, polyisoprene, styrene / butadiene copolymer. The rubber composition according to claim 5, which is a rubber, a silicone rubber, or a combination thereof. 7. The method according to claim 5, wherein the organic rubber as the component (B) is ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated polyene copolymer rubber, butyl rubber, acrylic rubber, or a combination thereof. Rubber composition. 8. The cross-linking agent of component (C) is sulfur, sulfur donor, low sulfur and high vulcanization accelerator, quinoid, peroxide, Si group-containing compound or resin.
The rubber composition according to any one of claims 1 to 7, 9. The rubber composition according to claim 1, further comprising a silanol condensation catalyst as the component (D). 10. The rubber composition according to claim 9, wherein the silanol condensation catalyst as the component (D) is a tin compound. 11. The rubber composition according to claim 9, wherein the silanol condensation catalyst as the component (D) is an aluminum compound and / or a titanium compound. 12. A crosslinked rubber elastic body obtained by crosslinking the rubber composition according to claim 1. 13. (A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula (1), wherein the main chain does not substantially contain an unsaturated double bond, and (B) an organic rubber. And (C) a crosslinkable rubber composition containing the organic rubber crosslinking agent, wherein the rubber composition is used for electric / electronic parts, transportation equipment, civil engineering / architecture, medical use or recreational use. . 14. The use of electric / electronic parts is heavy electric parts,
Light electrical parts, sealing materials, potting materials, coating materials or adhesives for circuits and substrates of electric and electronic equipment;
14. The rubber composition according to claim 13, which is a repair material for electric wire coating; an insulating seal material for electric wire joint parts; a roll for OA equipment; a vibration absorber; 15. The rubber composition according to claim 14, wherein the sealing material is used as a sealing material for refrigerators, freezers, washing machines, gas meters, microwave ovens, steam irons, or earth leakage breakers. 16. A potting material comprising a transformer high-voltage circuit, a printed circuit board, a high-voltage transformer with a variable resistor,
The rubber composition according to claim 14, which is used for potting an electrically insulating part, a semiconductive part, a conductive part, a solar cell, or a flyback transformer for a television. 17. The coating material is a high-voltage thick film resistor or a circuit element of a hybrid IC; HIC; an electrically insulating component; a semiconductive component; a conductive component; The rubber composition according to claim 14, which is used for coating a buffer material; a semiconductive element; or an optical fiber for optical communication. 18. The rubber composition according to claim 14, wherein the adhesive is used for bonding cathode ray tube wedges, necks, electrically insulating parts, semiconductive parts or conductive parts. 19. The crosslinkable rubber composition according to claim 13, wherein the use of the transport machine is the use of an automobile, a ship, an aircraft, or a railway vehicle. 20. The use of an automobile as a sealing material for a gasket, an electric component or an oil filter of an automobile engine; a botting material for an igniter HIC or an automobile hybrid IC; an automobile body, an automobile window glass, or an engine control board. 20. The rubber composition according to claim 19, which is an adhesive for a gasket for an oil pan, a gasket for a timing belt cover, a molding, a headlamp lens, a sunroof seal, or a mirror. 21. The rubber composition according to claim 19, wherein the use of the ship is a wiring connection branch box, a sealing material for electric system parts or electric wires; or an adhesive for electric wires or glass. 22. Civil engineering / architectural applications are associative joints of glass screen method for commercial buildings, joints around glass between sashes, interior joints in toilets, washrooms or showcases, joints around bathtubs, prefabricated houses. Sealants for building materials used for outer wall expansion joints for seams and joints for sizing boards; Sealants for double glazing; Sealants for civil engineering used for road repair; Paints for metals, glass, stone, slate, concrete or tile The rubber composition according to claim 13, which is used for an adhesive; or a pressure-sensitive adhesive sheet, a waterproof sheet, or a vibration-proof sheet. 23. The rubber composition according to claim 13, wherein the medical use is a sealing material for a medical rubber stopper, a syringe gasket, or a rubber stopper for a reduced-pressure blood vessel. 24. The rubber composition according to claim 13, wherein the leisure use is a swimming member for a swimming cap, diving mask or earplugs; or a gel cushioning member for sports shoes or baseball gloves. 25. (A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula (1) and containing substantially no unsaturated double bond in a main chain, (B) an organic rubber And (C) a sealing material comprising a crosslinkable rubber composition containing a crosslinking agent for the organic rubber. 26. (A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula (1) and containing substantially no unsaturated double bond in a main chain, (B) an organic rubber And (C) a potting material comprising a crosslinkable rubber composition containing the organic rubber crosslinking agent. 27. (A) an organic polymer having a hydrolyzable silyl group represented by the above general formula (1), wherein the main chain does not substantially contain an unsaturated double bond, and (B) an organic rubber. And (C) a coating material comprising a crosslinkable rubber composition comprising the organic rubber crosslinking agent. 28. (A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula (1), wherein the main chain does not substantially contain an unsaturated double bond, and (B) an organic rubber. And (C) an adhesive comprising a crosslinkable rubber composition containing the organic rubber crosslinking agent.