JP2016094551A - Room temperature-curable rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a room temperature-curable rubber composition which achieves both adhesion and moisture-proofness.SOLUTION: The room temperature-curable rubber composition contains: (A) an ethylene/α-olefin/nonconjugated polyene random copolymer which is liquid at room temperature; (B) a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule; (C) a hydrosilylation reaction catalyst; (D) a vinyl group-containing silane coupling agent; and (E) one or more organometallic compounds selected from the group consisting of organotitanium compounds, organozirconium compounds, and organoaluminum compounds.SELECTED DRAWING: None

Description

  The present invention relates to a room temperature curable rubber composition having both adhesiveness and moisture resistance.

  Conventionally, ethylene / α-olefin / non-conjugated polyene random copolymers such as ethylene-propylene-diene rubber (EPDM) have excellent functions such as weather resistance, heat resistance, moisture resistance, chemical resistance, etc. Used in various rubber products such as industrial products. However, the rubber-based curable composition has poor adhesion performance to various base materials, and when used as a potting material or coating material, moisture, chemicals, etc. invade from portions where the adhesive strength is insufficient. The various functions of the rubber-based curable composition could not be exhibited.

As a rubber composition excellent in moisture resistance, Patent Document 1 describes a rubber composition using a liquid ethylene / α-olefin / non-conjugated polyene random copolymer. However, the rubber composition described in Patent Document 1 has insufficient adhesion performance to various substrates.
In recent years, high chemical resistance is required in places such as production lines for precision machines. However, in order to improve the adhesion performance in rubber compositions such as Patent Document 1, it is necessary to use a primer. Even if it is used, there is a problem that it does not have sufficient adhesive performance and cannot secure chemical resistance of a precision machine. In addition, since the primer contains a solvent, the plastic substrate of the electronic component is often vulnerable to a solvent, and there is a possibility that a solvent crack may occur. In the production line of electronic parts, non-solvent is required, and it is not desirable to introduce a process including a solvent such as a primer.

  In addition, in the mirror glass of the bathroom, as it is used, there is a problem that moisture enters between the silver and the glass from the periphery of the mirror and becomes black due to irregular reflection. Therefore, there has been a demand for a composition having excellent moisture resistance for coating the peripheral part of the mirror, but only the rubber composition described in Patent Document 1 has insufficient adhesion performance and peels off due to its own weight. There was a problem that the moisture resistance of the mirror could not be secured.

JP 2013-14738 A

  An object of this invention is to provide the normal temperature curing type rubber composition which made adhesiveness and moisture-proof property compatible.

  In order to solve the above problems, the crosslinkable room temperature curable rubber composition of the present invention comprises (A) a room temperature liquid ethylene / α-olefin / nonconjugated polyene random copolymer, and (B) a hydrosilyl group. A hydrosilyl group-containing compound having at least two molecules in the molecule, (C) a catalyst for hydrosilylation reaction, (D) a vinyl group-containing silane coupling agent, (E) an organic titanium compound, an organic zirconium compound, and an organic aluminum A crosslinkable room temperature curable rubber composition comprising one or more organometallic compounds selected from the group consisting of compounds. In the present invention, 25 ° C. is referred to as normal temperature.

  The room temperature curable rubber composition of the present invention preferably further contains (F) a silane coupling agent other than the component (D).

  The rubber cured product of the present invention is obtained by crosslinking the rubber composition of the present invention by a hydrosilylation reaction.

  The first aspect of the product of the present invention is the one using the rubber composition of the present invention. The second aspect of the product of the present invention is a product using the rubber composition of the present invention as a coating agent. The third aspect of the product of the present invention is a product using the rubber composition of the present invention as a potting material.

  By using the rubber composition of the present invention, it is possible to obtain a product excellent in adhesiveness while maintaining moisture resistance (steam resistance). Moreover, since the rubber composition of the present invention is resistant to acids and bases, is excellent in chemical resistance, and is resistant to detergents, the life of the product can be extended. In addition, the rubber composition of the present invention is a room-temperature curable type that can be crosslinked at room temperature, so it can be cured without heating, can be used for adherends with low heat resistance, and has excellent adhesion performance. Therefore, no primer is required, and non-solvent, improvement in workability, and cost reduction can be achieved.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The crosslinkable room temperature curable rubber composition of the present invention comprises (A) a room temperature liquid ethylene / α-olefin / nonconjugated polyene random copolymer capable of crosslinking at room temperature and (B) a hydrosilyl group in one molecule. At least two hydrosilyl group-containing compounds, (C) hydrosilylation reaction catalyst, and (D) one or more organometallic compounds selected from the group consisting of organic titanium compounds, organic zirconium compounds, and organoaluminum compounds And (E) a vinyl group-containing silane coupling agent.

  The (A) normal temperature liquid ethylene / α-olefin / non-conjugated polyene random copolymer (also referred to as copolymer (A) in the present specification) capable of crosslinking at normal temperature is a structural unit derived from ethylene, It is a random copolymer containing a structural unit derived from an α-olefin and a structural unit derived from a non-conjugated polyene.

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

  In the copolymer (A), examples of the non-conjugated polyene include a chain non-conjugated diene, a cyclic non-conjugated diene, a triene, and the like. A cyclic non-conjugated diene is preferable, and a terminal vinyl group-containing norbornene compound is more preferable. preferable.

  As the terminal vinyl group-containing norbornene compound, a norbornene compound represented by the following formula (1) or a norbornene compound represented by the following formula (2) is preferable, and a norbornene compound represented by the following formula (1) is particularly preferable.

In said Formula (1), n is an integer of 0-10, Preferably it is an integer of 0-5. R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a 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 ¹ is preferably a hydrogen atom, a methyl group or an ethyl group. R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and specific examples of the alkyl group include alkyl groups having 1 to 5 carbon atoms among the specific examples of R ¹ described above. R ² is preferably a hydrogen atom, a methyl group or an ethyl group.

In the formula (2), R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and specific examples of the alkyl group include the same alkyl group as the above R ¹ .

  Examples of the norbornene compound represented by the formula (1) or (2) include 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- (5-heptenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3- Dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl) -5-hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) ) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexesyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) ) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene and the like. Among these, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) ) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (5-heptenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (7-octenyl)- 2-norbornene is preferred.

  Other cyclic non-conjugated dienes include, for example, methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl- Examples include 2-norbornene and dicyclopentadiene.

  Examples of the chain non-conjugated diene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5 -Dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene and the like.

  Examples of the triene include 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, and the like.

  These non-conjugated polyenes may be used alone or in combination of two or more. The proportion of the terminal vinyl group-containing norbornene compound in the non-conjugated polyene used is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more.

The molar ratio (ethylene / α-olefin) between the structural unit derived from ethylene and the structural unit derived from α-olefin in the copolymer (A) is preferably 35/65 to 95/5, and 40/60. ~ 90/10 is more preferable, and 45/55 to 85/15 is more preferable. When the molar ratio is within the above range, a rubber composition capable of providing a crosslinked rubber molded article having excellent adhesiveness, flexibility, heat aging resistance, strength properties and rubber elasticity, as well as cold resistance and processability is obtained. . The composition of the copolymer can be measured using, for example, ¹³ C-NMR.

  In addition, the content of the non-conjugated polyene in the copolymer (A) is preferably 0.05 to 8 mol%, more preferably 0.1 to 6 mol% in 100 mol% of the copolymer (A). 5-5 mol% is more preferable.

  The iodine value of the copolymer (A) is preferably 0.5 to 50 (g / 100 g), more preferably 1 to 40 (g / 100 g), and further preferably 5 to 30 (g / 100 g). When the iodine value is within the above range, a rubber composition having high crosslinking efficiency can be obtained, and the crosslinked rubber has excellent flexibility, heat resistance, compression set resistance, and environmental degradation resistance (heat aging resistance). A rubber composition capable of providing a molded body is obtained. Moreover, it can be made low-cost by making an iodine number into 50 or less.

  The intrinsic viscosity [η] measured in decalin at 135 ° C. of the copolymer (A) is preferably 0.01 to 5.0 (dl / g), and 0.01 to 2.0 (dl / g). Is more preferable, and 0.03-1.0 (dl / g) is preferable. When the intrinsic viscosity [η] is within the above range, a rubber composition is obtained that is excellent in fluidity and adhesion, excellent in strength properties and compression set resistance, and capable of providing a crosslinked rubber molded article excellent in processability. It is done. Further, when the intrinsic viscosity [η] is out of the range, for example, in the case of making it liquid, it is necessary to add a large amount of a plasticizer and a solvent. It may shift or the adhesive may deteriorate. In addition, the solvent may volatilize and the parts may become thin.

  Although the molecular weight (Mn) measured by the gel permeation chromatography (GPC) of the said copolymer (A) is not specifically limited, Preferably it is 100-10,000, More preferably, it is 500-5,000. The molecular weight distribution (Mw / Mn) is not particularly limited, but is preferably 1 to 200, more preferably 1.5 to 150. When the 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 preferable.

  The copolymer (A) is a room temperature liquid copolymer, preferably having a viscosity at 25 ° C. of 0.01 to 2,000 Pa · s, more preferably 0.01 to 1,000 Pa · s. . By setting the viscosity within the above range, workability and filling properties are good and a uniform compound can be obtained. The viscosity can be measured by the same method as that for the crosslinkable rubber composition according to the present invention.

  The copolymer (A) can be produced by copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene in the presence of a polymerization catalyst. For example, “Polymer manufacturing process (Industry Investigation Co., Ltd., publication p. 309-330), or Japanese Patent Laid-Open Nos. 9-71617, 9-71618, 9-208615, 10 -67823, JP-A-10-67824, JP-A-10-110054, and the like.

Examples of the method for producing the copolymer (A) include a catalyst containing a soluble vanadium compound represented by the following formulas (3) to (5) and an organoaluminum compound represented by the following formula (6) as main components. In the presence, a polymerization temperature of 30 to 60 ° C., particularly preferably 30 to 59 ° C., a polymerization pressure of 4 to 12 kgf / cm ² , particularly preferably 5 to 8 kgf / cm ² , a molar ratio of the supply amount of non-conjugated polyene and ethylene (Non-conjugated polyene / ethylene) This is carried out by randomly copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene under the condition of 0.01 to 0.2. The copolymerization reaction is preferably performed in a hydrocarbon medium.

VO (OR) _n X _3-n (3)
(In said formula (3), R is a hydrocarbon group, X is a halogen atom, and n is an integer of 0 or 1-3.)
VX ₄ (4)
(In formula (4), X is a halogen atom.)
V (OR) _c X _d (5)
(In Formula (5), R is a hydrocarbon group, and 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, and 3 ≦ c + d ≦ 4.)

R ′ _m AlX ′ _3-m (6)
(In said formula (6), R 'is a hydrocarbon group, X' is a halogen atom, and m is 1-3.)

The soluble vanadium compound is a component that is soluble in the hydrocarbon medium of the polymerization reaction system. For example, 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 (O-n-C 4 H 9) Cl 2, VO (OC 2 H 5) 3, VOBr 3, VCl 4, VOCl 3, VO (O-n-C 4 H ₉ ) ₃ , VCl ₃ · 2OC ₆ H ₁₂ OH and the like, or these electron donor adducts.

Specific examples of the organoaluminum compound include trialkylaluminum such as triethylaluminum, tributylaluminum and triisopropylaluminum; dialkylaluminum alkoxide such as diethylaluminum ethoxide and dibutylaluminum butoxide; ethylaluminum sesquiethoxide and butylaluminum sesquioxide. Alkylaluminum sesquialkoxides such as butoxide; partially alkoxylated alkylaluminums having an average composition represented by R ¹ _0.5 Al (OR ¹ ) _0.5, etc .; diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide Dialkylaluminum halides such as ethylaluminum sesquichloride, butylaluminum sesquichloride Partially halogenated alkylaluminums such as alkylaluminum sesquihalides such as lolide and ethylaluminum sesquibromide, ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide; diethylaluminum hydride and dibutylaluminum hydride Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as dialkylaluminum hydride, ethylaluminum dihydride, propylaluminum dihydride, etc .; moieties such as ethylaluminum ethoxychloride, butylaluminum butoxycyclide, ethylaluminum ethoxybromide Alkoxylated and halogenated alkylaluminium And the like.

  As the catalyst used in the copolymerization, a so-called metallocene catalyst, for example, a metallocene catalyst described in JP-A-9-40586 may be used.

  The copolymer (A) 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). The graft-modified copolymer (A) can be obtained by reacting the above-mentioned unmodified copolymer (A) with a polar monomer in the presence of a radical initiator.

  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-5. , 6-dicarboxylic acid and the like. Specific examples of the unsaturated carboxylic acid anhydride 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, ethyl methacrylate, dimethyl maleate, monomethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl citraconic acid, tetrahydro Examples thereof include dimethyl phthalate and dimethyl bicyclo (2,2,1) hept-2-ene-5,6-dicarboxylate. Among these, methyl acrylate and ethyl acrylate are preferable.

  The (B) hydrosilyl group-containing compound having at least 2, preferably 4 or more hydrosilyl groups in one molecule acts as a crosslinking agent that reacts with the copolymer (A). If the hydrosilyl group-containing compound (B) contains at least 2, preferably 3 or more, more preferably 4 or more, hydrogen atoms directly bonded to silicon atoms, that is, SiH groups in one molecule, the molecule The structure is not particularly limited, and any conventionally produced resinous material such as a linear, annular, branched structure or three-dimensional network structure can be used.

  The hydrosilyl group-containing compound (B) is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 75 parts by mass, and still more preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the copolymer (A). It is used in a proportion of 50 parts by mass, more preferably 0.2-30 parts by mass, particularly preferably 0.2-20 parts by mass. Within the above range, it is possible to obtain a rubber composition that is excellent in compression set resistance and can form a crosslinked rubber molded article having an appropriate crosslinking density and excellent strength and elongation properties. Use of the hydrosilyl group-containing compound (B) in a proportion exceeding 100 parts by mass is not preferable because it is disadvantageous in terms of cost.

As the hydrosilyl group-containing compound (B), a compound represented by the following formula (7) can be usually used.
R ⁴ _b H _c SiO _{(4-b-c) / 2} (7)
In the formula (7), R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, excluding an aliphatic unsaturated bond. In addition to the alkyl group exemplified for R1, a phenyl group and a halogen-substituted alkyl group such as a trifluoropropyl group can be exemplified. Of these, a methyl group, an ethyl group, a propyl group, a phenyl group, and a trifluoropropyl group are preferable, and a methyl group and a phenyl group are particularly preferable.
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 an organohydrogenpolysiloxane having preferably 2 to 1000, particularly preferably 2 to 300, most preferably 2 to 200 silicon atoms in one molecule. For example, siloxane oligomer such as 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyltetracyclosiloxane, 1,3,5,7,8-pentamethylpentacyclosiloxane; Trimethylsiloxy group-capped methylhydrogen polysiloxane, both ends of the molecular chain Trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, molecular chain both-end silanol group-capped methylhydrogen polysiloxane, molecular chain both-end silanol Base-blocked dimethylsiloxane methylhydride Gensiloxane copolymer, dimethylhydrogensiloxy group-capped dimethylpolysiloxane with molecular chain at both ends, dimethylhydrogensiloxy group-capped methylhydrogenpolysiloxane with molecular chain at both ends, dimethylhydrogensiloxy group-capped dimethylsiloxane / methyl with molecular chain at both ends Hydrogen siloxane copolymer, comprising R ⁴ ₂ (H) SiO _1/2 units and SiO _4/2 units, optionally R ⁴ ₃ SiO _1/2 units, R ⁴ ₂ SiO _2/2 units, R ⁴ Mention may be made, for example, of silicone resins which may contain (H) SiO _2/2 units, (H) SiO _3/2 or R ⁴ SiO _3/2 units.

Examples of the methyl hydrogen polysiloxane blocked with trimethylsiloxy groups at both ends of the molecular chain include, for example, a compound represented by the following formula (8), and further a part or all of the methyl groups in the formula (8): ethyl group, propyl group, And compounds substituted with a phenyl group, a trifluoropropyl group, and the like.
_{(CH 3) 3 SiO - (} - SiH (CH 3) -O-) d -Si (CH 3) 3 ··· (8)
(D in Formula (8) is an integer of 2 or more.)

The trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer at both ends of the molecular chain includes a compound represented by the following formula (9), and further a part or all of the methyl group in the following formula (10) is an ethyl group, Examples include compounds substituted with a propyl group, a phenyl group, a trifluoropropyl group, and the like.
_{(CH 3) 3 SiO - (} - Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 3 ··· (9)
(In formula (9), e is an integer of 1 or more, and f is an integer of 2 or more.)

Examples of the silanol group-blocked methyl hydrogen polysiloxane having both molecular chains at both ends include, for example, a hydrosilyl group-containing compound represented by the following formula (10), and further a part or all of the methyl group in the formula (10) is an ethyl group, a propyl group, And compounds substituted with a phenyl group, a trifluoropropyl group, and the like.
_{HOSi (CH 3) 2 O -} (- SiH (CH 3) -O-) 2 -Si (CH 3) 2 OH ··· (10)

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 (11), and further a part or all of the methyl group in the following formula (11) is an ethyl group: , Propyl group, phenyl group, trifluoropropyl group and the like.
_{HOSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) f -Si (CH 3) 2 OH ··· (11)
(In formula (11), e is an integer of 1 or more, and f is an integer of 2 or more.)

Examples of the dimethylhydrogensiloxy group-blocked dimethylpolysiloxane having both ends of the molecular chain include, for example, a compound represented by the following formula (12), and further a part or all of the methyl group in the following formula (12): an ethyl group, a propyl group, And compounds substituted with a phenyl group, a trifluoropropyl group, and the like.
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e -Si (CH 3) 2 H ··· (12)
(E in the formula (12) is an integer of 1 or more.)

Examples of the dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane having both molecular chain terminals include, for example, a compound represented by the following formula (13), and further a part or all of the methyl group in the following formula (13) is an ethyl group or a propyl group: , A phenyl group, a trifluoropropyl group, and the like.
HSi (CH ₃ ) ₂ O — (— SiH (CH ₃ ) —O—) _e —Si (CH ₃ ) ₂ H (13)
(E in the formula (13) is an integer of 1 or more.)

Examples of dimethylsiloxane / methylhydrogensiloxane copolymers blocked with dimethylhydrogensiloxy groups at both ends of the molecular chain include, for example, a compound represented by the following formula (14), and further a part or all of methyl groups in the following formula (14): And compounds substituted with an ethyl group, a propyl group, a phenyl group, a trifluoropropyl group, and the like.
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) e - (- SiH (CH 3) -O-) h -Si (CH 3) 2 H ··· (14)
(E and h in formula (14) 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, which can be a terminal group. A compound containing a triorganosilyl group or a diorganohydrogensiloxy group, such as 1,3,3-tetramethyldisiloxane, in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid, methanesulfonic acid, and the like. It can be easily obtained by equilibrating at a temperature of about 0 ° C to + 40 ° C.

  The blending ratio of the (B) hydrosilyl group-containing compound (B) is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 75 parts by mass with respect to 100 parts by mass of the copolymer (A). Part, more preferably 0.1 to 50 parts by weight, particularly preferably 0.2 to 30 parts by weight. These hydrosilyl group-containing compounds (B) may be used alone or in combination.

  The catalyst for hydrosilylation reaction (C) is an addition reaction catalyst and promotes the addition reaction (alkene hydrosilylation reaction) between the alkenyl group in the copolymer (A) and the SiH group of the compound (B). There is no particular limitation as long as it is a catalyst, but an addition reaction catalyst comprising a platinum group element such as a platinum-based catalyst, a palladium-based catalyst, or a rhodium-based catalyst (such as a group 8 metal, a group 8 metal complex, a group 8 metal compound of the periodic table) Group 8 metal catalysts) are preferred. In the present invention, it is desirable to use a complex of a group 8 element metal of the periodic table and a compound containing a vinyl group and / or a carbonyl group. As the group 8 element metal of the periodic table, platinum is particularly preferable.

  The platinum-based catalyst may be a known catalyst used for addition-curing type curing, for example, a finely powdered metal platinum catalyst described in US Pat. No. 2,970,150, US Pat. No. 2,823. , 218, chloroplatinic acid catalyst, platinum and hydrocarbon complex compounds described in US Pat. No. 3,159,601 and US Pat. No. 159,662, US Pat. Complexes of chloroplatinic acid and olefins described in US Pat. No. 3,516,946, platinum and vinyl described in US Pat. No. 3,775,452 and US Pat. No. 3,814,780 Examples include complex compounds with 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.

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

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

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

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

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

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

  An example of using alcohol as a solvent is a platinum-octanal / octanol complex. By including these solvents, there are advantages such as easy handling of the catalyst and easy mixing with the rubber composition. Among the various catalysts listed above, a vinylmethyl cyclic siloxane solution of a platinum-carbonyl complex, a platinum-vinylmethyl cyclic siloxane complex, a platinum-divinyltetramethyldisiloxane complex, a platinum-octanal / octanol complex, etc. are preferred in practice. Among these, a platinum-carbonylvinylmethyl cyclic siloxane complex is particularly preferable.

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

  Examples of the catalyst other than the above include Lewis acid and cobalt carbonyl.

These catalysts can be used alone or in combination of two or more. The ratio of the periodic table group 8 element metal (preferably platinum) contained in these catalysts is usually 0.1 to 10% by mass, preferably 1 to 5% by mass, and more preferably 2 to 4% by mass.
(C) 0.01-10 mass parts is preferable with respect to 100 mass parts of copolymers (A), More preferably, it is 0.1-5 mass parts, More preferably, it is 0.1-3 mass parts. It is used in the ratio. By using within this range, it is possible to form a crosslinked rubber molded article having a moderate crosslinking density and excellent strength characteristics and elongation characteristics at low cost.

  As the vinyl group-containing silane coupling agent (D), a known silane coupling agent having a vinyl group as a functional group can be used, and examples thereof include trimethoxyvinylsilane, triethoxyvinylsilane, and tripropoxyvinylsilane. Trialkoxyvinylsilane; dialkoxyalkylvinylsilanes such as methyldimethoxyvinylsilane and methyldiethoxyvinylsilane; dialkoxyarylvinylsilanes such as di (tert-pentoxy) phenylvinylsilane and di (tert-butoxy) phenylvinylsilane; monoalkoxys such as dimethylmethoxyvinylsilane Dialkylvinylsilanes; monoalkoxydiaryls such as tert-butoxydiphenylvinylsilane and tert-pentoxydiphenylvinylsilane Nylsilanes; monoalkoxyalkylarylvinylsilanes such as tert-butoxymethylphenylvinylsilane and tert-butoxyethylphenylvinylsilane; substituted alkoxyvinylsilane compounds such as tris (β-methoxyethoxy) vinylsilane; Ethoxyvinylsilane is preferred and trimethoxyvinylsilane is most preferred.

  The blending ratio of the (D) vinyl group-containing silane coupling agent is such that the molar ratio of the copolymer (A) and the (D) vinyl group-containing silane coupling agent is 1: 0.001 to 1:10. It is preferable that the ratio is 1: 0.01 to 1: 1.

  In the one or more organometallic compounds selected from the group consisting of (E) an organotitanium compound, an organozirconium compound, and an organoaluminum compound, the organotitanium compound is a compound comprising titanium and an organic atomic group. , Titanium salts, alkoxides, complexes, cyclopentadienyl compounds, and the like. Specifically, titanium (II) acetate, titanium acetate (IV), titanium 2-ethylhexanoate, titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) n-propoxide, titanium (IV) isopropoxy , Titanium (IV) butoxide, titanium oxide (II) acetylacetonate, titanium oxide (IV) bis (acetylacetone), diisopropoxybis (methylacetoacetate) titanium (IV), diisopropoxybis (ethylacetoacetate) Titanium (IV), dibutoxybis (acetylacetonato) titanium (IV), tetraacetylacetonate titanium (IV), bis (cyclopentadienyl) titanium (IV), dicarbonylbis (cyclopentadienyl) titanium (II) , Chlorobis (cyclopentadienyl) titanium ( V), dichlorobis (cyclopentadienyl) titanium (IV), bis (cyclopentadienyl) dimethyltitanium (IV), trichloro (cyclopentadienyl) titanium (IV), trichloro (pentamethylcyclopentadienyl) titanium (IV), trichloro (methyl) titanium (IV) tetrabenzyl titanium (IV), titanium (IV) 2-ethyl-1-hexanolate, isopropoxy (2-ethyl-1,3-hexanediolato) titanium, diiso Propoxybis (triethanolaminato) titanium, di (2-ethylhexoxy) bis (2-ethyl-1,3-hexanediolato) titanium, di-n-butoxybis (triethanolaminato) titanium, hydroxybis ( Lactone) titanium and the like.

  In the present invention, the organotitanium compound is preferably selected from a complex containing one or more selected from titanium carboxylate, alkoxide, alcohol and β-diketone as one component of the chelate-type ligand. At least one compound. Examples of the carboxylic acid include acetic acid, 2-ethylhexanoic acid, and naphthenic acid. Examples of the alkoxide include alkoxides composed of methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol and the like.

  As the titanium complex, a complex containing one or more selected from alcohol and β-diketone as one component of the chelate ligand is preferably used. Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol and the like. Furthermore, examples of the β-diketone include acetylacetone, methyl acetoacetate, ethyl acetoacetate, and benzoylacetone.

  The organic zirconium compound is a compound composed of zirconium and an organic atomic group, and includes a zirconium salt, an alkoxide, a complex, a cyclopentadienyl compound, and the like. Specifically, zirconium naphthenate, zirconium acetate (IV), zirconium 2-ethylhexanoate (IV), zirconium (IV) ethoxide, zirconium (IV) isopropoxide, zirconium (IV) n-propoxide, zirconium (IV) t-butoxide, tetranormal butoxyzirconium, butoxybis (methylacetoacetate) zirconium, butoxybis (ethylacetoacetate) zirconium, diisopropoxybis (ethylacetoacetate) zirconium, acetylacetone tributoxyzirconium, zirconium ( IV) Acetylacetonate, zirconium hexafluoroacetylacetonate, tetrakis (2,4-pentanedionato) zirconium (IV), dichlorobis (sic) Pentadienyl) zirconium (IV), bis (cyclopentadienyl) dimethylzirconium (IV), butadiene bis (cyclopentadienyl) zirconium (II), dicarbonylbis (cyclopentadienyl) zirconium (II), tribromo (cyclo Pentadienyl) zirconium (IV), tetrabenzylzirconium (IV) and the like.

  In the present invention, the organozirconium compound is preferably selected from complexes containing one or more selected from zirconium carboxylates, alkoxides, alcohols and β-diketones as one component of the chelate ligand. At least one compound. Examples of the carboxylic acid include acetic acid, 2-ethylhexanoic acid, and naphthenic acid. Examples of the alkoxide include alkoxides composed of methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butanol. As the zirconium complex, a complex containing one or more selected from alcohol and β-diketone as one component of the chelate ligand is preferably used. Examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol and the like. Furthermore, examples of β-diketone include acetylacetone, ethylacetoacetate, benzoylacetone, and the like.

  The organoaluminum compound is a compound composed of aluminum and an organic atomic group, and includes an aluminum salt, an alkoxide, a complex, and the like. Specifically, aluminum 2-ethylhexanoate, aluminum lactate, aluminum stearate, aluminum ethoxide, aluminum isopropoxide, aluminum n-butoxide, aluminum t-butoxide, aluminum trifluoroacetylacetonate, aluminum hexafluoroacetylacetonate , Tris (2,4-pentanedionato) aluminum, tris (acetylacetonato) aluminum and the like.

In the rubber composition of the present invention, the blending ratio of one or more organometallic compounds selected from the group consisting of (E) an organotitanium compound, an organozirconium compound, and an organoaluminum compound is (B) a vinyl group-containing silane. The molar ratio of the system coupling agent to the (E) organometallic compound is preferably 1: 0.001 to 1:10, and more preferably 1: 0.01 to 1: 5.
The said metal organic compound may be used independently and may be used in combination of 2 or more types.

  The crosslinkable room temperature curable rubber composition of the present invention is liquid at room temperature and preferably has a viscosity at 25 ° C. of 0.001 to 1000 Pa · s, more preferably 0.01 at 23 ° C. To 100 Pa · s, more preferably 0.01 to 10 Pa · s, and particularly preferably 0.01 to 3.0 Pa · s from the viewpoint of workability. The viscosity can be measured, for example, based on JIS K7117-1 (B type viscosity) or JIS K7117-1 (E type viscosity).

The rubber composition of the present invention has a silane coupling agent other than the components (F) and (D) (also referred to herein as (F) other silane coupling agent), that is, a vinyl group as a functional group. It is preferable to further add a silane coupling agent having no other functional group. The (F) other silane coupling agent may further improve the adhesion to a specific substrate.
As the (F) other silane coupling agent, various known silane coupling agents having other functional groups excluding a vinyl group as a functional group can be used. For example, γ-glycidoxypropyltri Epoxy group-containing silanes such as methoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-methacryloyloxypropyl (Meth) acryloyl group-containing silanes such as trimethoxysilane and γ-acryloyloxypropylmethyldimethoxysilane; isocyanate group-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; tetramethoxysilane, Te Traethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t -Tetraalkoxysilanes such as tetraalkoxysilane (tetraalkylsilicate) such as butoxysilane, and silicates such as partial hydrolysis condensates thereof; isocyanurate silanes such as tris (3-trimethoxysilylpropyl) isocyanurate Urea group-containing silanes such as γ-ureidopropyltrimethoxysilane and γ-ureidopropyltriethoxysilane; methyl [3-trimethoxysilyl] propyl] carbamate, 3- (triethoxysilyl) propylcarba Urethane group-containing silanes such as ethyl imidoate; 3-triethoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl succinic anhydride, 3-methyldimethoxysilylpropyl succinic anhydride, methyldiethoxysilylpropyl succinic acid Acid anhydride group-containing silanes such as acid anhydride and 1-carboxy-3-triethoxysilylpropyl succinic anhydride; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxy Silane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyl Dimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane Emissions, aminomethyl trimethoxy silane, and an amino group-containing silanes such as amino methyl dimethoxy silane.

  Since addition of amino group-containing silanes to the rubber composition of the present invention may inhibit curing, it is preferable to add silanes other than amino group-containing silanes. As such silanes, epoxy group-containing silanes, (meth) acryloyl group-containing silanes, isocyanate group-containing silanes, silicates, urea group-containing silanes, urethane group-containing silanes, acid anhydride group-containing silanes Can be mentioned.

  The room temperature curable rubber composition of the present invention includes a reaction inhibitor, a filler, a plasticizer, a softening agent, an antiaging agent, a processing aid, an organic peroxide, a crosslinking aid, a crosslinking aid, if necessary. Additives such as a foaming agent, a foaming aid, a colorant, a dispersant, a flame retardant, and a moisture supplement can be blended.

  Examples of the inhibitor include benzotriazole, ethynyl group-containing alcohols (eg, 1-ethynyl-2-ethyl-1-hexanol, ethynylcyclohexanol), acrylonitrile, amide compounds (eg, 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, tetramethyltetravinylcyclotetrasiloxane, organic peroxides such as hydroperoxide, etc. Is mentioned.

As the filler, a known filler such as a rubber reinforcing agent or an inorganic filler can be used.
Although it does not specifically limit as a rubber reinforcing agent, For example, these are surface-treated by carbon black, graphite, a silane coupling agent, etc., such as SRF, GPF, FEF, HAF, ISAF, SAF, FT, MT. Oxide fillers such as carbon black, fine powder silicic acid, silica, alumina, magnesium oxide, barium oxide, calcium oxide, hydroxide fillers such as aluminum hydroxide and magnesium hydroxide, sedimentary rock fillers such as diatomaceous earth and limestone, Examples thereof include clay mineral fillers such as kaolinite and montmorillonite, magnetic fillers such as ferrite, iron and cobalt, and conductive fillers such as silver, gold, copper and alloys.

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 the silica (BET method) is not particularly limited, is preferably ^{50 m} 2 / g or more, more preferably 100 to 400 m ² / g.

  The inorganic filler is not particularly limited, and examples thereof include light calcium carbonate, heavy calcium carbonate, talc, and clay.

  Examples of the plasticizer include paraffinic process oil, naphthenic process oil, aromatic process oil, ethylene and α-olefin co-oligomer, paraffin wax, liquid paraffin, white oil, petrolatum, lubricating oil, petroleum asphalt, petroleum jelly, etc. Petroleum softeners; coal tar softeners such as coal tar and coal tar pitch; fatty oil softeners such as castor oil, linseed oil, rapeseed oil and coconut oil; tall oil; petroleum resin, atactic polypropylene, Synthetic polymer materials such as malonindene resin; phthalic acid derivatives, isophthalic acid derivatives, tetrahydrophthalic acid derivatives, adipic acid derivatives, azelaic acid derivatives, sebacic acid derivatives, dodecane-2-acid derivatives, maleic acid derivatives, fumaric acid derivatives, Trimellitic acid derivative, pyromelli Tolic acid derivatives, citric acid derivatives, itaconic acid derivatives, oleic acid derivatives, ricinoleic acid derivatives, stearic acid derivatives, phosphoric acid derivatives, sulfonic acid derivatives, glycerin derivatives, glutaric acid derivatives, epoxy derivatives, glycol derivatives, paraffin derivatives, silicone oil And so on.

  As the softener, a softener usually used for rubber can be used. Specifically, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly; coal-tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fat oil-based softeners such as coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; petroleum Examples thereof include synthetic polymer materials such as resins, atactic polypropylene, and coumarone indene resins. Of these, petroleum softeners are preferably used, and process oil is particularly preferably used.

  Examples of the anti-aging agent include amine-based, hindered phenol-based, and sulfur-based anti-aging agents.

  Examples of processing aids include known compounds used in normal rubber processing, such as higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid, lauric acid; barium stearate, zinc stearate, calcium stearate. And salts of higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid, lauric acid, and the like.

  In the present invention, both addition crosslinking and radical crosslinking may be performed using an organic peroxide in addition to the catalyst used in the hydrosilylation reaction, depending on the intended use of the crosslinked product. When using an organic peroxide, it is preferable to use a crosslinking aid in combination.

  Although it does not specifically limit as a foaming agent, For example, inorganic foaming agents, such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, 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, toluene Sulfonyl hydrazide compounds such as sulfonyl hydrazide, p, p′-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3,3′-disulfonyl hydrazide; calcium azide, 4,4-diphenyldisulfonyl Disilazide, azide compounds such as p- toluenesulfonyl Le azide; carbon dioxide, nitrogen, oxygen, such as a gas such as chlorofluorocarbon and the like.

  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.

Examples of moisture supplements (water binders) include trialkyl orthoformate such as trimethyl orthoformate, triethyl orthoformate and tributyl orthoformate; trialkyl orthoacetates such as trimethyl orthoacetate, triethyl orthoacetate and tributyl orthoacetate, phenyl Monoisocyanate compounds such as isocyanate, p-chlorophenyl isocyanate, p-toluenesulfonyl isocyanate, tetraethyl silicate ((C ₂ H ₅ O—) ₄ Si), calcium carbonate, calcium hydroxide, Examples include silica gel, and some of them act as silane coupling agents.

Moreover, you may blend other well-known rubber | gum in the rubber composition of this invention in the range which does not impair the objective of this invention.
Other rubbers include, for example, natural rubber (NR), isoprene rubber such as isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber ( And conjugated diene rubbers such as CR).
Furthermore, a conventionally known ethylene / α-olefin copolymer rubber different from the copolymer (A) can also be used. Examples of such rubber include an ethylene / propylene random copolymer (EPR) and an ethylene / α-olefin / polyene copolymer (for example, EPDM).

  Moreover, in this invention, the hydrosilyl group containing compound which has one hydrosilyl group in 1 molecule may be included in the range which does not impair the objective of this invention.

  The method for producing the rubber composition of the present invention is not particularly limited. For example, a predetermined amount of the components (A) to (E) is blended, and other blending substances are blended as necessary, followed by deaeration and stirring. Can be manufactured. There is no particular limitation on the order of blending each component and other compounding substances, and it may be determined as appropriate.

The rubber composition of the present invention can be used as it is uncrosslinked, but is preferably used as a cured rubber obtained by crosslinking by a hydrosilylation reaction.
The rubber composition of the present invention can be cured at room temperature and is suitably used as a room temperature curable curable composition. However, if necessary, curing may be accelerated by heating as appropriate.

  The product of the present invention is a product produced by using the rubber composition of the present invention, and can be suitably used for applications around water such as electronic circuits, electronic parts, building materials, automobiles, bathroom mirrors, etc. is there.

  The room temperature curable rubber composition of the present invention comprises a coating agent, a potting material, a sealing agent, an adhesive, an adhesive, a binder, a paint, a vibration control material, a high rebound material, a dental impression material, a hose, a roll, and a light control material. It can be widely used for various applications such as sanitary goods or gaskets (or packings), and is particularly suitably used as a coating agent, a cover agent, or a potting material.

  The room temperature curable rubber composition of the present invention is suitably used for electronic circuits, electronic parts, building materials, automobiles, piping and the like. Moreover, the room temperature curable rubber composition of the present invention has both adhesiveness and moisture resistance, and is particularly suitable for use around water such as bathroom mirrors where moisture resistance, steam resistance and adhesion are required. Is preferred.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

Example 1
Each compounding substance was mix | blended with the composition shown in Table 1, and the rubber composition was prepared. The test shown below was done with respect to the obtained rubber composition. The results are shown in Table 2.

In Table 1, the compounding quantity of each compounding substance is shown by g, and the details of the compounding substance are as follows.
* 1) PX062: Trade name of room temperature liquid ethylene / α-olefin / non-conjugated polyene random copolymer manufactured by Mitsui Chemicals, Inc.
* 2) X93-1346: trade name of a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule, manufactured by Shin-Etsu Chemical Co., Ltd.
* 3) 3% Pt-CTS-CTS: a trade name for a catalyst for hydrosilylation reaction, manufactured by NV Chemcat Co., Ltd.
* 4) KBE1003: Vinyltriethoxysilane, trade name of Shin-Etsu Chemical Co., Ltd.
* 5) KBM1003: Vinyltrimethoxysilane, trade name of Shin-Etsu Chemical Co., Ltd.
* 6) TC750: Titanium diisopropoxybisethyl acetoacetate, trade name of Matsumoto Fine Chemical Co., Ltd.
* 7) TA-10: Titanium tetraisopropoxide, trade name of Matsumoto Fine Chemical Co., Ltd.
* 8) Aluminum chelate D: Aluminum bisethyl acetoacetate / monoacetylacetonate, trade name of Matsumoto Fine Chemical Co., Ltd.
* 9) ZC-700: Zirconium tetraacetylacetonate, trade name of Matsumoto Fine Chemical Co., Ltd.
* 10) U800P: Dioctyltin oxide, trade name of Nitto Kasei Co., Ltd.
* 11) KBM403: 3-glycidoxypropyltrimethoxysilane, trade name of Shin-Etsu Chemical Co., Ltd.
* 12) Ethyl silicate 28P: trade name of tetraethoxysilane, manufactured by Colcoat Co., Ltd.

1) Adhesion test A rubber composition was applied to various adherends at 100 μm on both sides, and after taking an open time of 2 minutes, it was clamped with two pinches and cured at 80 ° C. for 1 day. The body was made. Using the prepared test body, a tensile test was performed under the condition of a tensile speed of 50 mm / min, and the tensile shear bond strength was measured.

2) Chemical resistance test The mirror coated with the rubber composition was immersed in various chemicals for a predetermined time and then subjected to a cross-cut test defined in JIS R3220 to confirm adhesion. Evaluation was performed according to the following evaluation criteria.
○: no peeling, ×: peeling

3) Water resistance test The mirror coated with the rubber composition was immersed in warm water at 60 ° C for a predetermined time and then subjected to a cross-cut test defined in JIS R3220 to confirm adhesion. Evaluation was performed according to the following evaluation criteria.
○: no peeling, ×: peeling

4) Moisture resistance test The mirror coated with the rubber composition was subjected to a cross-cut test defined in JIS R3220 after a predetermined time in an environment of room temperature 85 ° C and humidity 85% to confirm adhesion. Evaluation was performed according to the following evaluation criteria.
○: no peeling, ×: peeling

(Examples 2-8 and Comparative Examples 1-5)
A rubber composition was obtained by the same method except that the compounding substances were changed as shown in Table 1, and then the rubber composition was measured. The results are shown in Table 2.

  As shown in Table 2, the rubber composition of the present invention exhibited excellent adhesion to various adherends and was excellent in chemical resistance, water resistance and moisture resistance.

Claims (6)

(A) room temperature liquid ethylene / α-olefin / non-conjugated polyene random copolymer;
(B) a hydrosilyl group-containing compound having at least two hydrosilyl groups in one molecule;
(C) a catalyst for hydrosilylation reaction;
(D) a vinyl group-containing silane coupling agent;
(E) one or more organic metal compounds selected from the group consisting of organic titanium compounds, organic zirconium compounds, and organic aluminum compounds;
A cross-linkable room temperature curable rubber composition comprising: (F) The room temperature curable rubber composition according to claim 1, further comprising a silane coupling agent other than the component (D).   A rubber cured product obtained by crosslinking the rubber composition according to claim 1 or 2 by a hydrosilylation reaction.   A product comprising the rubber composition according to claim 1.   A product using the rubber composition according to claim 1 as a coating agent.   A product using the rubber composition according to claim 1 or 2 as a potting material.