JP2002037944A - Curable rubber composition and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable rubber composition which contains water or a metal salt hydrate as a water-supplying source necessary for curing the composition together with a silanol condensation catalyst, scarcely deteriorates its curability (curing speed) after stored, has a large curing speed and excellent weather resistance, can be compounded with a compound having an easily water-reacting reactive silicon group, such as a silane coupling agent, does not cause a cross-linking reaction during storage, and does not raise the viscosity of the composition. SOLUTION: This two-part type or multi-part type curable rubber composition characterized by comprising at least two liquids of (I) a main agent comprising (A) a silyl group-containing ethylene/α-olefin/non-conjugated polyene random copolymer rubber whose non-conjugated polyene is a specific terminal vinyl group-containing norbornene compound and which contains specified hydrolysable silyl groups in the molecule and (II) a curing agent comprising (B) a silanol condensation catalyst and (C) water or a metal salt hydrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a silyl group having a structural unit derived from a specific non-conjugated polyene-containing norbornene compound having a terminal vinyl group and having a specific hydrolyzable silyl group in the molecule. Containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber
The present invention relates to a liquid or three or more liquid curable rubber composition and its use.

[0002]

BACKGROUND OF THE INVENTION A silicon-containing group having a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond (hereinafter also referred to as a reactive silicon group) is
For example, a group represented by -Si (OCH _{3) 3,} is a well known functional group. This functional group is a group that is hydrolyzed by moisture in the air and generates a siloxane bond (Si-O-Si) through a silanol condensation reaction with another reactive silicon group via -Si (OH) ₃ or the like.

[0003] (CH ₃ O) ₃ Si ~~~~~~~~ Si (OCH ₃ ) ₃ →
_{[(HO) 3 Si~~~~~~ (OH} ) 3] → (~~
O) ₃ Si ~~~~~~~~ Si (OSi ~~~) ₃ Therefore, the polymer having a reactive silicon group crosslinks and cures even at room temperature in the presence of moisture. Among these polymers, the rubber-based polymer having a main chain skeleton has a property of being a liquid having a high viscosity at room temperature and becoming a rubber elastic body by curing, and is widely used in architectural sealing materials and industrial sealing materials. Have been. The sealing material is used to fill gaps (joints) between building materials such as wall materials, harden and close the gaps, and maintain watertightness and airtightness.

[0004] Among such rubber polymers, saturated hydrocarbon polymers such as polyisobutylene are polymers that produce cured products having excellent weather resistance, heat resistance and gas barrier properties. However, since the gas barrier property is large, the moisture barrier property is large, and when curing with moisture in the air, there is a problem that although curing proceeds on the surface, it takes a long time of one week or more to cure to the inside. There has been proposed a composition having excellent deep curability, in which a hydrate of a metal salt is dispersed in the composition and rapidly cured to the inside at room temperature (JP-A-2-185565).

[0005] A polymer having a reactive silicon group is often used as a curable composition to which a silanol condensation catalyst as a curing catalyst, a filler, a plasticizer and the like are added. Curable compositions can be broadly classified into one-part curable compositions and two-part curable compositions. The one-part curable composition is a one-part liquid containing all of the above additives and is convenient because it does not need to be mixed at the time of use. However, the one-part curable composition is completely dehydrated so as not to be cured before use. It must be saved in a state. On the other hand, the two-part curable composition must be mixed at the time of use, which is inconvenient. However, even if there is some water, the presence of a silanol condensation catalyst makes it difficult to cure the polymer having a reactive silicon group. Complete dehydration is not required as a mold.

When a hydrate of the above metal salt is used as a water source for curing a polymer, a one-part curable composition cannot be obtained. This is because curing starts as soon as the polymer, the silanol condensation catalyst, and the hydrate of the metal salt are mixed. In addition, titanium compounds and tin compounds are often used as silanol condensation catalysts. Many of them are decomposed in the presence of water, and it is expected that the silanol condensation catalyst will be decomposed even by hydrates of metal salts. Therefore, when a hydrate of a metal salt is used as a water source, the hydrate of the metal salt is added to the curable composition immediately before use (curing), or the polymer component of the two-part composition is added. It is blended with the main ingredient.

[0007] However, it is inconvenient to mix only the metal salt hydrate immediately before use (hardening). In addition, when a hydrate of a metal salt is blended with the main component, there is a problem that the polymer having a reactive silicon group slightly hardens and the viscosity of the main component increases. Further, a silane coupling agent is often used as an adhesion-imparting agent in a sealing material or the like. However, since the silane coupling agent easily reacts with moisture, there is a problem that even if it is desired to use it as an additive, it cannot be blended with the main agent or the curing agent. For example, γ-
Isocyanatepropyltrimethoxysilane, ONCCH ₂ CH
A silane coupling agent such as ₂ CH ₂ Si (OCH ₃ ) ₃ reacts with a hydrate of a metal salt when added to a main agent, and is decomposed by a silanol condensation catalyst when added to a curing agent, and is used as a silane coupling agent. In addition, it does not act as an adhesion-imparting agent.

[0008] Japanese Patent Application Laid-Open No. 10-182,992 discloses a compound having a hydrolyzable group bonded to a silicon atom, such as moisture-curable polyisobutylene, and having a silicon-containing group which can be crosslinked by forming a siloxane bond. In a curable composition using a saturated hydrocarbon-based polymer and a metal salt hydrate that is a source of water, to provide one that does not increase the viscosity of the composition during storage, and furthermore, a silane coupling agent The invention of a curable composition for the purpose of providing a curable composition in which a compound having a reactive silicon group which easily reacts with moisture as described above can be blended is disclosed. In the present invention, a two-part or multi-part curable composition is prepared, and a metal salt hydrate is added to a curing agent containing a silanol condensation catalyst. That is, the curable composition according to the present invention is:
(A) a main agent containing a saturated hydrocarbon-based polymer having a hydrolyzable group bonded to a silicon atom and having a silicon-containing group capable of crosslinking by forming a siloxane bond;
(B) A two-component or multi-component curable composition comprising at least two components of a silanol condensation catalyst and a curing agent containing a metal salt hydrate.

However, the isobutylene-based polymer used as the saturated hydrocarbon-based polymer in the invention described in this publication is insufficient in curing speed and weather resistance, and therefore its improvement is desired. In this publication, a silyl group-containing ethylene-containing compound having a structural unit derived from a specific norbornene compound having a terminal vinyl group, which is a non-conjugated polyene, and having a specific hydrolyzable silyl group in the molecule. No two-part or three-part curable rubber composition containing an α-olefin / non-conjugated polyene random copolymer rubber is disclosed.

[0010]

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a novel curable rubber composition using a metal salt hydrate as a water supply source and its use. It is intended to provide. Another object of the present invention is to provide a curable rubber composition which does not increase in viscosity during storage, has a high curing rate, and is excellent in weather resistance, and its use.

Another object of the present invention is to provide a curable rubber composition to which a compound having a reactive silicon group which easily reacts with moisture, such as a silane coupling agent, can be compounded, and its use. .

[0012]

SUMMARY OF THE INVENTION The curable rubber composition according to the present invention has a structural unit derived from at least one kind of a norbornene compound having a terminal vinyl group represented by the following general formula [I] or [II], which is a non-conjugated polyene. And a main agent (I) containing a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) having a hydrolyzable silyl group represented by the following general formula [III] in the molecule: And a curing agent (II) containing a silanol condensation catalyst (B) and water or a metal salt hydrate (C), and a two-component or multi-component curable rubber composition comprising at least two components. It is characterized by having.

[0013]

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Wherein n is an integer of 0 to 10,
R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ]

[0015]

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

[0017]

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[Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group,
Alkoxyl group, acyloxy group, ketoxime group,
A hydrolyzable group selected from an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. As the silanol condensation catalyst (B), a tetravalent tin compound is desirable.

The tetravalent tin compound is preferably a dialkyltin dialkoxide. As the metal salt hydrate (C), a hydrate of an alkali metal salt or a hydrate of an alkaline earth metal salt can be used. In the present invention, the main agent (I) may further contain a silane coupling agent.

Examples of the silane coupling agent include a silicon-containing group having a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond, a primary amino group, a secondary amino group, and a Compounds having at least one group selected from the group consisting of a secondary amino group, an epoxy group, an isocyanate group and an isocyanurate are preferred.

In the curable rubber composition according to the present invention, a metal salt hydrate can be used as a water supply source, and the viscosity of the composition does not increase during storage. In addition, the curable rubber composition according to the present invention may contain a compound having a reactive silicon group that easily reacts with moisture, such as a silane coupling agent. The curable rubber composition according to the present invention hardly reduces the curability (curing speed) even after storage, and the hydrate of the metal salt is removed from the main agent side so that the viscosity of the main agent decreases, and the handling of the composition is reduced. There is also an advantage that can be easily performed.

Another curable rubber composition according to the present invention comprises an organic polymer containing a hydrolyzable silyl group represented by the general formula [III] and having substantially no unsaturated double bond in the main chain. A two-component type comprising at least two components: a main component (I) containing a coalesced (C), and a curing agent (II) containing a silanol condensation catalyst (B) and water or a metal salt hydrate (C). Alternatively, it is a multi-component type crosslinkable rubber composition characterized by being used for electric / electronic parts, transportation equipment, civil engineering / construction, medical or leisure uses.

Examples of the use of the electric / electronic parts include heavy electric parts, light electric parts, sealing materials, potting materials, coating materials or adhesives for circuits and boards of electric / electronic devices; repair materials for electric wire coatings; electric wire joints. Insulation sealing materials for parts; rolls for OA equipment; vibration absorbers; or encapsulants for gels or capacitors. The sealing material is used, for example, as a sealing material for refrigerators, freezers, washing machines, gas meters, microwave ovens, steam irons, or earth leakage breakers.

The potting material is used 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. Can be The coating material is a high voltage thick film resistor or a circuit element of a hybrid IC; HI
C: an electrically insulating component; a semiconductive component; a conductive component; a module; a printed circuit; a ceramic substrate; a buffer material of a diode, a transistor or a bonding wire; a semiconductive element; or an optical fiber for optical communication.

The adhesive is used to bond cathode ray tube wedges, necks, electrically insulating parts, semiconductive parts or conductive parts. Examples of the use of the transport machine include a car, a ship, an aircraft, and a railway vehicle. Specific examples of the use of the automobile include a sealing material for a gasket, an electrical component or an oil filter of an automobile engine; a potting material for an igniter HIC or a hybrid IC for an automobile; an automobile body, a window glass for an automobile, or an engine control board. Coatings for oil pans, gaskets for oil pans, gaskets for timing belt covers, adhesives for moldings, headlamp lenses, sunroof seals or mirrors.

Specific examples of the use of the ship include the use of 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 civil and architectural uses include a joint joint of a glass screen method for 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 outer wall expansion joints and sizing board joints; Sealants for double glazing; Sealants for civil engineering used for road repair; Paints and adhesives for metals, glass, stone, slate, concrete or tile Or used for adhesive sheets, waterproof sheets or vibration-proof sheets.

Examples of the medical use include sealing materials for rubber stoppers for pharmaceuticals, syringe gaskets, or rubber stoppers for reduced-pressure blood vessels. The leisure uses include, for example, swimming caps for swimming caps, diving masks or earplugs; or gel cushioning elements for sports shoes or baseball gloves.

The sealing material, the potting material, the coating material and the adhesive according to the present invention have the general formula [II]
I] An organic polymer (C) containing a hydrolyzable silyl group and having substantially no unsaturated double bond in the main chain.
Or a multi-part type, comprising at least two parts of a main agent (I) containing the following, and a curing agent (II) containing a silanol condensation catalyst (B) and water or a hydrate of a metal salt (C). Of a crosslinkable rubber composition.

Further, the foaming material composition according to the present invention is an organic polymer containing a hydrolyzable silyl group represented by the general formula [III] and having substantially no unsaturated double bond in the main chain. A two-component type comprising at least two components: a main component (I) containing (C) and a curing agent (II) containing a silanol condensation catalyst (B) and water or a hydrate of a metal salt (C). It is characterized by comprising a multi-component type crosslinkable rubber composition.

In the foam material composition, a gas generated at the time of condensation can be used as a foaming agent.

[0031]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the curable rubber composition according to the present invention and its use will be specifically described. The curable rubber composition according to the present invention is a two-part or multi-part curable rubber composition, and a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A)
And a curing agent (II) containing a silanol condensation catalyst (B) and water or a hydrate of a metal salt (C). The main agent (I) may further contain a silane coupling agent.

Main agent (I) [Silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A)] Silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer used in the present invention The rubber (A) has the following general formula [III]
A hydrosilation reaction (hydrosilylation reaction) of a specific silicon compound with a specific ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ) containing a hydrolyzable silyl group represented by Can be obtained.

[0033]

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In the general formula [III], R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably a monovalent hydrocarbon group having no aliphatic unsaturated bond. For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group, and a part or all of the hydrogen atoms bonded to these carbon atoms Examples thereof include a group substituted with a halogen atom such as a fluorine atom.

X is a hydride group (-H), a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, a thioalkoxy group,
Or an amino group. Halogen group, alkoxyl group,
Specific examples of the acyloxy group, the ketoxime group, the acid amide group, and the thioalkoxy group include the same groups as the specific examples of these groups in X in the general formula [IV] described below.

A is an integer of 0, 1 or 2, and is preferably 0 or 1. Ethylene, α-olefin and non-conjugated polyene random
Polymer Rubber (A ₀ ) The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ) used in the present invention comprises ethylene and
It is a random copolymer of an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene.

As the α-olefin having 3 to 20 carbon atoms, 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,
Examples thereof include 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. 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 can be used alone or in combination of two or more. The non-conjugated polyene used in the present invention has the following general formula [I] or [I
I] is a norbornene compound having a vinyl group at the terminal.

[0039]

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In the general formula [I], n is 0 to 10
R ¹ is a hydrogen atom or a carbon atom having 1 to 1
0 alkyl group, and as the alkyl group having 1 to 10 carbon atoms for R ¹ , specifically, a methyl group, an ethyl group,
Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, hexyl, isohexyl, heptyl, Examples include an octyl group, a nonyl group, and a decyl group.

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

[0042]

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In the general formula [II], R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group of R ³ include the same alkyl groups as the specific examples of the alkyl group of R ¹ . As the norbornene compound represented by the general formula [I] or [II], specifically, 5-methylene-2-norbornene,
5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5-
(1-methyl-2-propenyl) -2-norbornene, 5- (4-
Pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene , 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5-
(6-heptenyl) -2-norbornene, 5- (3-methyl-5-
Hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-
Pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene , 5- (1,2-dimethyl-5-hexesyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene and the like. Among them, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) ) -2-norbornene, 5-
(5-hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene and 5- (7-octenyl) -2-norbornene are preferred. These norbornene compounds can be used alone or in combination of two or more.

The above norbornene compound such as 5-vinyl
In addition to 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, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, Linear non-conjugated dienes such as 4,5-dimethyl-1,4-hexadiene and 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene,
5-methylene-2-norbornene, 5-isopropylidene-2-
Cyclic non-conjugated dienes such as norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene- And trienes such as 3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.

Ethylene / α comprising the above components
-The olefin / non-conjugated polyene random copolymer rubber (A ₀ ) has the following properties. (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 (A ₀ ) is (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) in a proportion of 40/60 to 95/5, preferably 50/50 to 9
0/10, more preferably 55/45 to 85/15,
Particularly preferably, they are contained at a molar ratio of [(a) / (b)] of 60/40 to 80/20.

When the molar ratio is within the above range, a rubber composition which is excellent in heat aging resistance, strength characteristics and rubber elasticity and can provide a crosslinked 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 (A ₀ ) 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 / 1 g).
00g).

When the iodine value is within the above range, the content of the hydrolyzable silyl group can be adjusted to the desired content, and the compression set is excellent, and the environmental deterioration resistance (= heat aging resistance) is excellent. Thus, a rubber composition capable of providing a crosslinked rubber molded article can be 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 (A ₀ ) measured in decalin at 135 ° C. is 0.001 to 2 dl / g, preferably 0. 01 to 2 dl / g, more preferably 0.05 to
1.0 dl / g, more preferably 0.05 to 0.7 dl
/ G, particularly preferably 0.1 to 0.5 dl / g.

When the intrinsic viscosity [η] is within the above range, a rubber composition excellent in fluidity, which can provide a crosslinked rubber molded article excellent in strength properties and compression set resistance, can be obtained. (Iv) Molecular weight distribution (Mw / Mn) The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ) measured by GPC is 3 to 100, preferably 3. 3-7
5, more preferably 3.5 to 50.

When the molecular weight distribution (Mw / 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 (A ₀ ) used in the present invention has a polymerization temperature of 30 to 30 in the presence of a catalyst containing the following compounds (H) and (I) as main components. 60 ° C., especially 30-59 ° C., polymerization pressure 4-12 kgf / cm ² , especially 5-8 kgf / c
m ² , ethylene, an α-olefin having 3 to 20 carbon atoms, and a general molar ratio of non-conjugated polyene and ethylene (non-conjugated polyene / ethylene) of 0.01 to 0.2. It is obtained by random copolymerization with a norbornene compound having a terminal vinyl group represented by the formula [I] or [II]. The copolymerization is preferably carried out in a hydrocarbon medium. (H) VO (OR) _n X _3-n (where R
Is a hydrocarbon group, X is a halogen atom, and n is 0
Or a soluble vanadium compound represented by the formula: VX ₄ (X is a halogen atom)
A vanadium compound represented by the formula:

The above-mentioned soluble vanadium compound (H) is a component soluble in a hydrocarbon medium of a polymerization reaction system, and specifically, has the general formula VO (OR) aXb or V (OR) cXd
(Where R is a hydrocarbon group, 0 ≦ a ≦ 3, 0 ≦ b ≦
3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c
+ D.ltoreq.4), or an electron donor adduct thereof.

More specifically, VOCl ₃ , VO (OC _{2
H 5) Cl 2, VO (} OC 2 H 5) 2 Cl, VO (O-iso-
_{C 3 H 7) Cl 2,} VO (O-n-C 4 H 9) Cl 2, VO (O
_{C 2 H 5) 3, VOBr} 3, VCl 4, VOCl 3, VO (O
—N—C ₄ H ₉ ) ₃ and VCl ₃ .2OC ₆ H ₁₂ OH. (I) R ′ _m AlX ′ _3-m (R ′ is a hydrocarbon group and 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; ethoxide, alkyl sesquichloride alkoxides such as butyl sesquichloride butoxide; R ¹ _0.5 Al
(OR ¹ ) a partially alkoxylated alkylaluminum having an average composition represented by _0.5 or the like; a dialkylaluminum halide such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride; Partially halogenated alkylaluminums such as alkylaluminum sesquihalides such as ethylaluminum sesquibromide, alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide; diethylaluminum hydride, dibutylaluminum hydride and the like Dialkyl aluminum hydride, ethyl aluminum dihydride, propyl alcohol Partially hydrogenated alkyl aluminum such as alkylaluminum dihydride such as ruminium dihydride; partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide Can be mentioned.

In the present invention, a soluble vanadium compound represented by VOCl ₃ among the above compound (H) and Al (OC ₂ H ₅ ) ₂ Cl among the above compound (I)
When a blend of / Al ₂ (OC ₂ H ₅ ) ₃ Cl ₃ (blend ratio is 1/5 or more) is used as a catalyst component, after Soxhlet extraction (solvent: boiling xylene, extraction time: 3 hours, mesh: 325) Is preferred because an ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ) having an insoluble content of 1% or less can be obtained.

As a catalyst used in the above copolymerization, a so-called metallocene catalyst such as disclosed in JP-A-9-405 is used.
No. 86, the metallocene catalyst may be used. Silicon Compound The silicon compound used in the present invention has the following general formula [IV]
Is represented by

[0055]

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In the general formula [IV], R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably a monovalent hydrocarbon group having no aliphatic unsaturated bond; For example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and a cyclohexyl group, an aryl group such as a phenyl group and a tolyl group, and a part or all of the hydrogen atoms bonded to these carbon atoms are fluorine atoms And the like.

X represents a hydride group (-H), a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group, a thioalkoxy group,
Or an amino group. Examples of the halogen group include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.

Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, a propoxybutoxy group, an isopropoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group and a phenoxy group. , And the like. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

Examples of the ketoximate group include an acetoxymate group, a dimethylketoxime group, a dimethylketoxime group, a cyclohexylmate group and the like. 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, thioisobutoxy, sec-thiobutoxy, tert-thiobutoxy, thiopentyloxy, thiohexyloxy, and thiophenoxy. 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, alkoxyl groups, especially those having 1 to carbon atoms
4 alkoxyl groups are preferred. A in the general formula [IV] is an integer of 0, 1 or 2, and is preferably 0 or 1.

Specific examples of the silicon compound represented by the general formula [IV] include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, diethylchlorosilane, phenyldichlorosilane and diphenylchlorosilane. Kind;
Alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldimethoxysilane, ethyldimethoxysilane, butyldimethoxysilane, methyldiethoxysilane, ethyldiethoxysilane, butylethoxysilane, phenyldimethoxysilane; triacetoxysilane, methyldiacetoxy Acyloxysilanes such as silane and phenyldiacetoxysilane; ketoximes such as tris (acetoxymate) silane, bis (dimethylketoxime) methylsilane, bis (methylethylketoxime) methylsilane and bis (cyclohexylketoxime) methylsilane Silanes; aminoxysilane,
Examples include aminooxysilanes such as triaminoxysilane; aminosilanes such as methyldiaminosilane and triaminosilane. Of these, alkoxysilanes are particularly desirable.

The silicon compound represented by the above general formula [IV] is used in an amount of 0.01 to 5 mol per mol of the double bond in the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ). , Preferably 0.05 to 3 mol. The hydrosilylation reaction is
The reaction is performed using a catalyst of a transition metal complex. As such a 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 10 as a metal unit with respect to the reactant (ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ )). 000 ppm, preferably 1-10
00 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. In addition, this hydrosilylation reaction can be performed under pressure, if necessary. Reaction time is 10 seconds to 10
About an hour.

In this reaction, a solvent may or may not be used, but when used, an inert solvent such as ethers and hydrocarbons is preferable. In the present invention,
By the hydrosilylation reaction, ethylene α
-Containing a hydrolyzable silyl group as described below, wherein a SiH group of a silicon compound represented by the above general formula [IV] is added to a double bond in an olefin / non-conjugated polyene random copolymer rubber (A ₀ ). The ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) is obtained.

[0065]

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[0066]

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The hydrolyzable silyl group-containing compound represented by the above general formula [IV] is added with a hydrogen-modified siloxane having one terminal represented by the following formula to obtain weather resistance, slipperiness, and gas characteristics characteristic of the siloxane. It is also possible to impart transparency.

[0068]

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(In the formula, R ¹ is a group represented by R in the general formula [IV]
Similarly to the above, it is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and particularly preferably an alkyl group. Further, m is an integer of 5 to 200, particularly 10 to 1
An integer of 50 is preferred. ) Curing Agent (II) The curing agent (II) used in the present invention contains a silanol condensation catalyst (B) and water or a hydrate of a metal salt (C).

[Silanol Condensation Catalyst (B)] As the silanol condensation catalyst (B) which is one of the components of the curing agent (II) used in the present invention, conventionally known ones can be used. Are titanates such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutyl Malate, dibutyltin diisooctyl malate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate,
Tin carboxylate salts such as dibutyltin diacetate, tin octylate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate, dioctyltin diversate, tin naphthenate; dibutyltin dimethoxide, dibutyl Tin alkoxides such as tin diphenoxide and dibutyltin diisopropoxide; dibutyltin oxide;
Tin oxides such as dioctyltin oxide; reaction products of dibutyltin oxide with phthalic acid esters; dibutyltin bisacetylacetonate; organic compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate Aluminum compounds; Chelating compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; Lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylene Tetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine Min, 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 of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; excess polyamines and epoxy compounds Silanol condensation catalysts such as silane coupling agents having an amino group such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane; and other acidic catalysts And known silanol condensation catalysts such as basic catalysts.

When rapid curing at room temperature is required among these catalysts, it is preferable to use a tetravalent tin compound, especially dialkoxytin dialkoxide, especially dibutyltin bisacetylacetonate, dibutyltin dimethoxide, Dibutyltin dipropoxide is preferred. A tetravalent tin compound such as dialkyltin dialkoxide hardly deactivates when mixed with water or a hydrate of a metal salt (at the curing agent side), and the curing rate decreases even after storage. Therefore, when a tetravalent tin compound is used as a curing catalyst, the effect of the present invention is remarkably exhibited.

These catalysts can be used alone or in combination.
It can be used in combination of more than one kind. Curing agent (II)
The compounding amount of the silanol curing catalyst (B) in the component is preferably based on 100 parts by weight of the silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) in the main component (I). It is about 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight. If the amount of the silanol curing catalyst (B) is less than this range, the curing speed may be slow, and the curing reaction may not be sufficiently advanced. On the other hand, when the amount of the silanol curing catalyst (B) exceeds this range, local heat generation and foaming occur during curing, making it difficult to obtain a good cured product, and also shortening the pot life, resulting in workability. Is also not preferred.

[Hydrate of water or metal salt (C)] Among the hydrates of water or metal salt (C) in the curing agent (II) used in the present invention, the hydrate of metal salt is , Main agent (I)
It acts as a supply source of water necessary for condensation and curing of the silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) in the component, and promotes formation of a crosslinked structure.

As such hydrates of metal salts, commercially available ones can be widely used, and examples thereof include hydrates of alkaline earth metal salts and hydrates of other metal salts. Can be Specifically, Al ₂ O ₃ .H ₂ O, Al ₂ O ₃
3H ₂ O, Al ₂ (SO ₄ ) ₃ · 18H ₂ O, Al ₂ (C _{2
O 4) 3 · 4H 2 O} , AlNa (SO 4) 2 · 12H 2 O, A
1K (SO ₄ ) ₂ · 12H ₂ O, BaCl ₂ · 2H ₂ O, B
_{a (OH) 2 · 8H 2} O, CaSO 4 · 2H 2 O, CaS 2
_{O 3 · 6H 2 O, Ca} (NO 3) 2 · 4H 2 O, CaHPO 4
・ 2H ₂ O, Ca (C ₂ O ₄ ) .H ₂ O, Co (NO ₃ ) _{2.
6H 2 O, Co (CH 3} COO) 2 · 4H 2 O, CuCl 2
・ 2H ₂ O, CuSO ₄ .5H ₂ O, FeCl ₂ .4H
_{2 O, FeCl 3 · 6H 2} O, FeSO 4 · 7H 2 O, Fe
(NH ₄ ) (SO ₄ ) ₂ · 12H ₂ O, K ₂ CO ₃ · 1.5H
_{2 O, KNaCO 3 · 6H 2} O, LiBr · 2H 2 O, Li
_{2 SO 4 · H 2 O,} MgSO 4 · H 2 O, MgSO 4 · 7H 2
_{O, MgHPO 4 · 7H 2 O} , Mg 3 (PO 4) 2 · 8H
₂ O, MgCO ₃ .3H ₂ O, Mg ₄ (CO ₃ ) ₃ (OH) ₂
3H ₂ O, MoO ₃ 2H ₂ O, NaBr 2H ₂ O, N
_{a 2 SO 3 · 7H 2 O} , Na 2 SO 4 · 10H 2 O, Na 2 S 2
_{O 3 · 5H 2 O, Na} 2 S 2 O 6 · 2H 2 O, Na 2 B 4 O 7 ·
_{10H 2 O, NaHPHO 3 · 2.5H} 2 O, Na 3 PO 4
_{· 12H 2 O, Na 2 CO} 3 · H 2 O, Na 2 CO 3 · 7H 2
O, Na ₂ CO ₃ · 10H ₂ O, NaCH ₃ COO · 3H _{2
O, NaHC 2 O 4 · H} 2 O, NiSO 4 · 6H 2 O, Ni
_{C 2 O 4 · 2H 2 O} , SnO 2 · nH 2 O, NiC 2 O 4 · 2
_{H 2 O, Sn (SO 4} ) 2 · 2H 2 O, ZnSO 3 · 2H
_{3 O, ZnSO 4 · 7H 2} O, Zn 3 (PO 4) 2 · 4H
₂ O, Zn (CH ₃ COO) ₂ .2H ₂ O and the like.

[0075] Among these, preferred hydrates and hydrates of alkaline earth metal salts of an alkali metal salt, _{specifically, MgSO 4 · 7H 2 O,} Na 2 CO 3 · 10H 2 O,
Na ₂ SO ₄ · 10H ₂ O, Na ₂ S ₂ O ₃ · 5H ₂ O, Na ₃
PO ₄ .12H ₂ O, Na ₂ B ₄ O ₇ .10H ₂ O and the like are preferably used. The metal salt hydrates described above can be used alone or in combination of two or more.

When water is used, the water used in the present invention is preferably 0.1 to 100 parts by weight of the silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). 01 to 25 parts by weight, more preferably 0.05 to 15 parts by weight, still more preferably 0.2 to 25 parts by weight
It is desirable to use at a ratio of up to 5 parts by weight. The hydrate of the metal salt is preferably 0.01 to 100 parts by weight of the silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) containing a hydrolyzable silyl group. -50 parts by weight, more preferably 0.1-3
It is desirable to use 0 parts by weight, more preferably 1 to 20 parts by weight, particularly preferably 2 to 10 parts by weight.

The above-mentioned hydrates of water and metal salts are each 1
These can be used alone or in combination of two or more. Other Components The curable rubber composition according to the present invention may contain various additives. A typical additive is an adhesion-imparting agent. A typical example thereof is a silane coupling agent. However, an adhesion-imparting agent other than the silane coupling agent can also be used.

The silane coupling agent is a compound having a group containing a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as a hydrolyzable silicon group) and a functional group other than the group. Examples of the hydrolyzable silicon group include groups represented by the following general formula (1), preferably the following general formula (2).

[0079]

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In the general formula (1), R ¹ and R ² are
Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or (R ′) ₃ SiO— (R ′) is each independently A substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms).

X is a hydrolyzable group. further,
a is 0, 1, 2, or 3, and b is 0, 1, 2,
And a and b do not become 0 at the same time. M is 0 or an integer of 1 to 19. In the general formula (2), R ² , X, and a are the same as R ² , X, and a in the general formula (1), respectively.

Examples of such a hydrolyzable group include a hydrogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group,
Commonly used groups such as a mercapto group and an alkenyloxy group are exemplified, and a methoxy group and an ethoxy group are preferred from the viewpoint of a high hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly preferably 3 or more.

Examples of the functional group other than the hydrolyzable silicon group include primary, secondary, and tertiary amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, and halogens. be able to. Of these, primary, secondary, and tertiary amino groups, epoxy groups, isocyanate groups, isocyanurates, and the like are preferable, and isocyanate groups and epoxy groups are particularly preferable.

Specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxysilane. Methoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ-ureidopropylpropyl Amino group-containing silanes such as trimethoxysilane, n-β- (n-vinylbenzylaminoethyl) -γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane; γ-mercaptopropyltrimethoxysilane, γ -Mercaptopropyltriethoxysilane, γ-mercaptopropylmethyl Mercapto group-containing silanes such as methoxysilane and γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β -(3,4-Epoxycyclohexyl)
Epoxy group-containing silanes such as ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, n-β- (n-carboxymethylaminoethyl) -γ-
Carboxysilanes such as aminopropyltrimethoxysilane; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acroyloxypropylmethyltriethoxysilane ;
halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; isocyanate-containing silanes such as γ-isocyanatopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane And the like.

[0085] Amino-modified silyl polymers, silylated amino polymers, unsaturated amino silane complexes, blocked isocyanate silanes, phenylamino long-chain alkyl silanes, amino silylated silicones, silylated polyesters, and the like, which are derivatives of these modified silane cups, are also available. It can be used as a ring agent. Such a silane coupling agent is easily decomposed in the presence of moisture, but can be present in a stable state when added to the main component (I) of the curable rubber composition according to the present invention.

Further, as an adhesion-imparting agent other than the silane coupling agent, a compound having an epoxy group or an isocyanate group in a molecule (including a polymer of isocyanate) may of course be used. The above-mentioned adhesiveness-imparting agents can be used alone or in combination of two or more.

In the present invention, the adhesion-imparting agent is used in an amount of 0.1 to 100 parts by weight of the silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A).
It is used in an amount of from 0.01 to 20 parts by weight, particularly preferably from 0.1 to 10 parts by weight. The curable rubber composition according to the present invention can be further modified by blending various fillers.

As such a filler, specifically,
Reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, talc, carbon black; heavy calcium carbonate, colloidal calcium carbonate, diatomaceous earth, calcined clay, clay, titanium oxide, bentonite, organic bentonite And fillers such as ferric oxide, zinc oxide and activated zinc white; and fibrous fillers such as glass fibers and filaments.

When it is desired to obtain a curable rubber composition having high strength by using these fillers, it is necessary to mainly use reinforcing agents such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, talc, carbon black and the like. The filler is used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) in the main component (I) used in the present invention. If used, a cured product having high strength and high modulus in mechanical properties can be obtained.

On the other hand, when it is desired to obtain a cured product having a low modulus and a high elongation, heavy calcium carbonate, colloidal calcium carbonate, diatomaceous earth, calcined clay, clay, titanium oxide,
Fillers such as bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, etc. are used as the main agent (I) component used in the present invention, and a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer is used. The rubber (A) may be used in a proportion of 5 to 400 parts by weight with respect to 100 parts by weight.

The above-mentioned fillers may be used alone or in combination.
It can be used in combination of more than one kind. The filler may be added to the main component (I) component, may be added to the curing agent (II) component, or may be the main component (I) component and the curing agent (II).
It may be added to both of the components. In the curable rubber composition according to the present invention, when a plasticizer is used in combination with a filler, it is more useful because the elongation of the cured product can be increased and a large amount of the filler can be mixed.

As such a plasticizer, commonly used plasticizers can be used, and those having good compatibility with the silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) can be used. preferable. Specific examples of the plasticizer include process oil, polybutene, hydrogenated polybutene, α-methylstyrene oligomer, liquid polybutadiene, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, and atactic polypropylene. Among them, hydrocarbon compounds such as process oil containing no unsaturated bond, hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, and naphthenic oil are preferable.

Examples of the plasticizer include process oil, paraffin oil, naphthenic oil, polybutadiene, ethylene α-
Olefin oligomers and the like can be mentioned. The plasticizer is used to introduce a hydrolyzable silyl group into the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ).
It may be used in place of the solvent for the purpose of adjusting the reaction temperature, adjusting the viscosity of the reaction system, and the like.

Further, the curable rubber composition according to the present invention may contain, if necessary, an antioxidant, an ultraviolet absorber, a light stabilizer, a flame retardant, a thixotropic agent, a pigment, and a surfactant. And the like can be appropriately added as long as the object of the present invention is not impaired. In the curable rubber composition according to the present invention, either a two-part composition or a three-part or more composition is possible. When used as a two-part composition, for example, the main agent (I) of the present invention to which a filler, a plasticizer, and the like are added;
Separated from the curing agent (II) of the present invention to which a filler, a plasticizer, and the like are added, and when both are mixed and used immediately before use, the initial cured material properties are stably exhibited even after long-term storage. be able to.

The curable rubber composition according to the present invention is mainly useful as an elastic curable composition, and can be used for sealing applications such as electronic electricity, civil engineering, waterproofing, buildings, ships, automobiles and roads. it can. In addition, non-primer glass,
It can be used as various types of adhesive compositions for firm adhesion to a wide range of substrates such as stone, ceramic, wood, synthetic resin, metal and the like.

The curable rubber composition according to the present invention is particularly useful as a sealing material for double glazing, and is useful for float glass, surface-treated various heat ray reflecting glasses, and spacers such as pure aluminum and anodized aluminum. And exhibit stable adhesiveness over a long period of time. Curable Rubber Composition and Use Thereof The curable rubber composition according to the present invention contains a hydrolyzable silyl group-containing ethylene / α-olefin /
Including the curable composition containing the non-conjugated polyene random copolymer rubber as the component (A), the curable composition contains the following curable composition, that is, contains a hydrolyzable silyl group represented by the general formula [III]. A main agent (I) containing an organic polymer (D) having substantially no unsaturated double bond in the main chain, and a silanol condensation catalyst (B) and water or a hydrate of a metal salt (C). A curable rubber composition comprising at least two components of a curing agent (II) containing:
It is suitably used for civil engineering / architecture, medical or leisure use, and the like.

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 substrates 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 sealing material is, for example, a refrigerator, a freezer, a washing machine,
It is suitably used as a sealing material for 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 part, a semiconductive part, a conductive part, a solar cell or a flyback transformer for a television. Used for The coating material is, for example, various circuit elements such as a high-voltage thick film resistor or a hybrid IC; HIC, an electrical insulating component; a semiconductive component;
Printed circuit; ceramic substrate; buffer material such as diode, transistor or bonding wire; semiconductive element; or optical fiber for optical communication.

The above-mentioned adhesive is suitably used, for example, for bonding cathode ray tube wedges, necks, electrically insulating parts, semiconductive parts or conductive parts. Examples of the use of the transport machine include a car, a ship, an aircraft, and a railway vehicle. Applications for automobiles include, for example, gaskets for automobile engines, sealing materials for electrical components or oil filters; potting materials for igniter HICs or hybrid ICs for automobiles; coating materials for automobile bodies, window glasses for automobiles, engine control boards; Alternatively, a gasket such as a timing belt cover, a molding, a headlamp lens, a sunroof seal, an adhesive for a mirror, or the like may be used.

Examples of the use of the ship include a wiring junction box, a sealing material for electric system components 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 medicines, 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 curable rubber composition according to the present invention can be used
In applications such as electronic components, transports, civil engineering, leisure, etc., it can be suitably used as a sealing material (sealing material), a potting material, a coating material, and an adhesive.

[0103]

The curable rubber composition according to the present invention contains water or a metal salt hydrate together with a silanol condensation catalyst as a supply source of water required for curing. (Curing speed) hardly decreases, and the curing speed is high and the weather resistance is excellent. In addition, the curable rubber composition according to the present invention can further contain a compound having a reactive silicon group that easily reacts with water, such as a silane coupling agent, and the composition does not undergo a crosslinking reaction during storage. Does not increase in viscosity.

[0104]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. Examples, the composition of the copolymer rubber used in the reference examples,
Iodine value, intrinsic viscosity [η], molecular weight distribution (Mw / Mn)
Was measured or determined by the following method. (1) Composition of copolymer rubber The composition of the copolymer rubber was measured by ¹³ C-NMR method. (2) Iodine value of copolymer rubber The iodine value of the copolymer rubber was determined by a titration method. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of the copolymer rubber was measured in decalin at 135 ° C. (4) Molecular Weight Distribution (Mw / Mn) The molecular weight distribution of the copolymer rubber was determined by the ratio (Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by GPC.
w / Mn). For GPC, GMH-HT and GMH-HTL manufactured by Tosoh Corporation were used for the column, and orthodichlorobenzene was used for the solvent.

The curing rate test and accelerated weathering test performed in Examples and Reference Examples were performed according to the following methods. (1) Curing speed test The curable composition (raw material) was molded (20 × 80 × 5 m).
m) and cured for 24 hours at 23 ° C. and 50% RH.

Next, the cured product obtained as described above was peeled off, and the thickness of the cured portion was measured to the nearest 0.1 mm using a dial gauge having a weak spring force. When the measured thickness was 5 mm or more, the evaluation of the curing speed was represented by ○ when the measured thickness was less than 5 mm. (2) Accelerated weathering test A weathering test was performed using a sunshine carbon arc weatherometer in accordance with JIS B-7753.

<Test conditions> Irradiation / rain cycle: 120 minutes irradiation / 18 minutes rain Black panel temperature: 63 ± 2 ° C Temperature in tank: 40 ± 2 ° C Irradiation time: 500 hours

[0108]

[Production Example 1] [Silyl group-containing ethylene / propylene / 5-
Vinyl-2-norbornene random copolymer rubber (A-
Production of 1)] A polymerization vessel made of stainless steel and having a substantial inner volume of 100 liters equipped with a stirring blade (stirring rotation speed = 250 rpm)
Using ethylene, propylene and 5-vinyl-2
-Terpolymerization with norbornene was carried out. 60 liters of hexane, 2.5 kg of ethylene, 4.0 kg of propylene, 4.0 kg of 5-vinyl-2-norbornene at a rate of 380 g of hydrogen, 700 liters of hydrogen, and VO OEt) ₂ Cl and Al (Et) _1.5 Cl _1.5 were continuously fed at a rate of 45 mmol and 315 mmol, respectively.

When the copolymerization reaction was carried out under the conditions described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A ₀ -1) 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 performed.

The ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A ₀ -1) obtained as described above has an ethylene content of 68 mol%,
Intrinsic viscosity [η] measured in decalin at 35 ° C is 0.2 d
1 / g, the iodine value (IV) was 10 (g / 100 g), and the Mw / Mn was 15. To 100 g of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A ₀ -1) obtained as described above, 0.3 g of a 2% chloroplatinic acid solution in toluene was added, and methyldimethoxysilane was added. 1.5 g was charged and reacted at 120 ° C. for 2 hours. After the reaction, it was distilled off excess methyl dimethoxy silane and a solvent (toluene), dimethoxymethylsilyl group _{(-SiCH 3 (OCH 3) 2} ) Ethylene-propylene-5-vinyl-2-norbornene random copolymerization containing 1 to 1.5 g of the combined rubber (A-1) was obtained.

[0111]

[Production Example 2] [Production of Saturated Hydrocarbon Polymer] Into a 1-liter autoclave made of pressure-resistant glass, 7.5 mmol of p-DCC (the following compound A) was placed, and a stirring blade, a three-way cock and a vacuum line were placed. After the attachment, the inside was replaced with nitrogen.

Then, while flowing nitrogen from one of the three-way cocks, the solvent, which was dried by molecular sieve treatment in an autoclave using a syringe and toluene 330 m
1, hexane 141 ml, and then the additive α-
3.0 mmol of picoline was added. Next, a liquefied gas sampling tube made of pressure-resistant glass with a needle valve containing 113 g of isobutylene dehydrated by passing through a column filled with barium oxide was connected to a three-way cock. It was immersed in an acetone bath and cooled for 1 hour while stirring the inside of the polymerization vessel. After cooling, the inside of the reactor was depressurized by a vacuum line, and then the needle valve was opened. Isobutylene was introduced into the polymerization vessel from a pressure-resistant glass liquefied gas sampling tube. Thereafter, the pressure was returned to normal pressure by flowing nitrogen from one of the three-way cocks.

Next, it was confirmed that the inside of the polymerization vessel was stable at −70 ° C., and 7.18 g (3.8 mmol) of TiCl ₄ was added from a three-way cock using a syringe to start polymerization. After 2 hours, 2.57 g (22.5 mmol) of allyltrimethylsilane was added. After an additional hour of reaction, the catalyst was deactivated by pouring the reaction mixture into water. Next, the organic layer was washed with pure water three times and then separated, and the solvent was distilled off under reduced pressure to obtain an allyl-terminated isobutylene polymer.

The structure of Compound A is as shown below.

[0115]

Embedded image

Next, 100 g of the obtained allyl-terminated isobutylene polymer was dissolved in 50 ml of n-heptane.
After the temperature was raised to about 70 ° C., methyl dimethoxysilane 1.
2 [eq. / Allyl group], platinum (vinyl siloxane) complex 1 × 10 ^-4 [eq. / Allyl group] was added to carry out a hydrosilylation reaction. The reaction was followed by FT-IR, and after confirming that the absorption derived from olefin at 1640 cm ^-1 had disappeared in about 4 hours, the reaction was stopped.

Next, the reaction solution was concentrated under reduced pressure to obtain an isobutylene polymer having reactive silicon at both terminals represented by the following formula.

[0118]

Embedded image

The yield was calculated from the yield of the polymer obtained as described above, and the number average molecular weight (Mn) and Mw / Mn were determined by the GPC method.
Protons belonging to each structure by 0 MHz ¹ H-NMR analysis (protons derived from initiator: 6.5 to 7.5 ppm,
Methyl protons bonded to silicon atoms from polymer ends: 0.0-0.1 ppm, and methoxy protons:
It was determined by measuring and comparing the intensities of the resonance signals of 3.5 to 3.4). The analytical value of the polymer was Mn = 11141.
6, Mn / Mw = 1.47, Fn (silyl) = 1.95
(The number average molecular weight is a relative value using a polystyrene standard product, and Fn (silyl) is the number of terminal silyl functional groups per 1 molecule of isobutylene polymer).

[0120]

Example 1 100 parts by weight of the silyl group-containing ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) obtained in Production Example 1 was added to a paraffinic process oil [Idemitsu Kosan ( 90 parts by weight, Diana Process PS-32], heavy calcium carbonate [PO320B] 1, manufactured by Shiroishi Calcium Co., Ltd.
80 parts by weight, colloidal calcium carbonate [manufactured by Shiraishi Industry Co., Ltd.
50 parts by weight of trade name EDS-D10A, 100 parts by weight of talc (trade name LMR, manufactured by Maruo Calcium Co., Ltd.), 1 part by weight of antioxidant 1 [trade name: Irganox 1010, manufactured by Ciba Geigy Co., Ltd.] 2 [Sumisorb 400 manufactured by Sumitomo Chemical Co., Ltd., 1 part by weight, anti-aging agent 3] Sankyo LS-76 manufactured by Sankyo
5] 1 part by weight, 3 parts by weight of light stabilizer [manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sandant NBC], 3 parts by weight of photocurable resin [manufactured by Toagosei Co., Ltd., trade name: Alonix M400], thixo 5 parts by weight of a property imparting agent [Kusumoto Kasei Co., Ltd. product name, Dispalon # 305], silane coupling agent γ
-4 parts by weight of isocyanatepropyltriethoxysilane [manufactured by Nippon Unicar Co., Ltd., trade name: Y-9030] was added, and the mixture was kneaded well with a three-paint roll to obtain a base material of Reference Example 1.

Further, as a silanol condensation catalyst, 4 parts by weight of dibutyltin bisacetylacetonate (trade name: U-220, manufactured by Nitto Kasei Co., Ltd.), sodium sulfate (Na ₂ SO ₄ .10H)
₂ O) 4 parts by weight, paraffinic process oil [Diana Process PS-32, manufactured by Idemitsu Kosan Co., Ltd.]
0 parts by weight, heavy calcium carbonate [Maruo Calcium Co., Ltd.
Manufactured by Snow Light SS], 20 parts by weight, carbon black [Mitsubishi Kasei Co., Ltd., trade name: CB # 30]
After manually mixing and kneading 2.5 parts by weight in a disposable cup, using an Excel Auto Homogenizer manufactured by Nippon Seiki Seisaku-sho at a speed of 10,000 rpm and a speed of 10,000 rpm.
The operation of stirring for 3 minutes was performed three times to prepare the curing agent of Example 1.

The above composition was placed in a sealed glass bottle and stored for one month in a perfect oven at 50 ° C.
The viscosity of the base was measured. The viscosity is measured by Tokyo Keiki Co., Ltd.
No. was measured with a B-type viscometer (BS type). Using a rotor of No. 7 at 23 ° C. 10r of main agent immediately after main agent preparation
The pm viscosity was 8525 poise. The 10 rpm viscosity of the base material after storage was 9020 poise.

[0123]

Reference Examples 1-2 Paraffin-based process oil [Diana Process PS-32, trade name, manufactured by Idemitsu Kosan Co., Ltd.] 90 per 100 parts by weight of the polymer obtained in Production Example 2
Parts by weight, heavy calcium carbonate [Shiroishi Calcium Co., Ltd.]
180 parts by weight, manufactured by Shiraishi Kogyo Co., Ltd., trade name: EDS-D10
A] 50 parts, talc [manufactured by Maruo Calcium Co., Ltd., trade name: LMR] 100 parts by weight, antioxidant 1 [manufactured by Ciba Geigy Co., Ltd., trade name: Irganox 1010] 1 part by weight, antioxidant 2 [Sumitomo Chemical] 1 part by weight, manufactured by Sumisorb 400 (trade name), 1 part by weight of antioxidant 3 [manufactured by Sankyo Co., Ltd., Sanol LS-765], and 1 part by weight of light stabilizer [manufactured by Sanshin Chemical Industry Co., Ltd.] Name Sandant NBC] 3 parts by weight, photocurable resin [Toagosei Co., Ltd., trade name Alonix M400] 3 parts by weight, thixotropic agent [Kusumoto Kasei Co., Ltd., trade name Dispalon # 305] 5 parts by weight ,
Silane coupling agent γ-isocyanatopropyltriethoxysilane [trade name Y- manufactured by Nippon Unicar Co., Ltd.]
9030], and kneaded well with a three-paint roll to obtain a base material of Reference Example 1.

Further, as a silanol condensation catalyst, 4 parts by weight of dibutyltin bisacetylacetonate [trade name: U-220, manufactured by Nitto Kasei Co., Ltd.], sodium sulfate (Na ₂ SO ₄ .10H)
₂ O) 4 parts by weight, paraffinic process oil [Diana Process PS-32, manufactured by Idemitsu Kosan Co., Ltd.]
0 parts by weight, heavy calcium carbonate [Maruo Calcium Co., Ltd.
Manufactured by Snow Light SS], 20 parts by weight, carbon black [Mitsubishi Kasei Co., Ltd., trade name: CB # 30]
After manually mixing and kneading 2.5 parts by weight in a disposable cup, using an Excel Auto Homogenizer manufactured by Nippon Seiki Seisaku-sho at a speed of 10,000 rpm and a speed of 10,000 rpm.
The operation of stirring for 3 minutes was performed three times to prepare the curing agent of Reference Example 1.

Further, as Reference Example 2, the base material obtained by adding 4 parts by weight of sodium sulfate (Na ₂ SO ₄ · 10H ₂ O) to the base material of Reference Example 1 and the one obtained by adding no sodium sulfate to the curing agent of Reference Example 1 were used. As a curing agent, the same test as in Reference Example 1 was used. Each of the above compositions was placed in a sealed glass bottle, stored in a perfect oven at 50 ° C. for one month, and the viscosity of the main ingredient was measured.

The viscosity was measured with a B-type viscometer (BS type) manufactured by Tokyo Keiki Co., Ltd. 23 ° C using a 7 rotor
Performed at The viscosity of 10 rpm of the base material immediately after the preparation of the base material was 7632 poise in Reference Examples 1 and 2, and 8
It was 928 poise. In addition, 10 rp of the main agent after storage
The m viscosity was 9072 poise in Reference Example 1 and Reference Example 2, respectively, and was not less than the measurement limit (12,000 poise or more).
Thereby, when the hydrate of the metal salt is blended in the main agent, the viscosity of the main agent itself becomes higher than when the hydrate of the metal salt is not added to the main agent, and when stored, the viscosity of the main agent increases. You can see that.

[0127]

Example 2 The ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A) obtained in Production Example 1
-1) 100 parts by weight of paraffinic process oil [Diana Process PS manufactured by Idemitsu Kosan Co., Ltd.
-32], 90 parts by weight, heavy calcium carbonate [manufactured by Shiraishi Calcium Co., Ltd., trade name PO320B], 180 parts by weight,
Colloidal calcium carbonate [Shiraishi Industry Co., Ltd., trade name ED
S-D10A] 50 parts by weight, talc [manufactured by Maruo Calcium Co., Ltd., trade name LMR] 100 parts by weight, antioxidant 1 [Ciba Geigy Co., Ltd. trade name, Irganox 1]
010] 1 part by weight, antioxidant 2 [Sumitomo Chemical Co., Ltd.
Brand name Sumisorb 400] 1 part by weight, antioxidant 3
1 part by weight (trade name, Sanol LS-765, manufactured by Sankyo Co., Ltd.), 3 parts by weight of light stabilizer [trade name: Sandant NBC, manufactured by Sanshin Chemical Industry Co., Ltd.], photocurable resin [Toagosei Co., Ltd.] 3 parts by weight of Aronix M400], 5 parts by weight of thixotropy-imparting agent [Dispalon # 305, trade name of Kusumoto Kasei Co., Ltd.], silane coupling agent γ-isocyanatopropyltriethoxysilane [Nihon Unicar Co., Ltd. And 4 parts by weight of trade name Y-9030] and 2 parts by weight of γ-glycidoxypropyltrimethoxysilane [trade name A-187 manufactured by Nippon Unicar Co., Ltd.] and kneaded well with three paint rolls. The main ingredient of Example 2 was used.

Further, as a silanol condensation catalyst, 4 parts by weight of dibutyltin bisacetylacetonate [trade name: U-220, manufactured by Nitto Kasei Co., Ltd.], sodium sulfate (Na ₂ SO ₄ .10H)
₂ O) 4 parts by weight, paraffin-based process oil [Diana Process PS-32, manufactured by Idemitsu Kosan Co., Ltd.) 10
Parts by weight, heavy calcium carbonate [Maruo Calcium Co., Ltd.
Manufactured by Snow Light SS], 20 parts by weight, carbon black [Mitsubishi Kasei Co., Ltd., trade name: CB # 30]
After manually mixing and kneading 2.5 parts by weight in a disposable cup, using an Excel Auto Homogenizer manufactured by Nippon Seiki Seisaku-sho at a speed of 10,000 rpm and a speed of 10,000 rpm.
The operation of stirring for 3 minutes was performed three times to prepare the curing agent of Example 2.

The above composition was placed in a sealed glass bottle and stored for one month in a perfect oven at 50 ° C.
The time-dependent changes in the adhesiveness to various substrates and the mechanical properties immediately after preparation of the composition and after storage were confirmed by the following test methods. The results are shown in Tables 1 and 2. The sample for the tensile test was prepared by assembling a glass or aluminum substrate into an H-shape according to the method for preparing a tensile adhesive test specimen specified in JIS A 5758-1992, and combining the above main agent and curing agent with the total number of parts by weight of the main agent component. The mixture was weighed so as to have a ratio to the total number of parts by weight of the curing agent component, kneaded sufficiently, filled with the compound, and then cured in an oven.

The curing conditions were as follows: 23 ° C. × 7 days + 50
° C x 7 days. The substrate used for the H-type tensile test is JIS
A Float glass conforming to A 5758-1992 [manufactured by Koensha: Designated by Japan Sealing Material Association, dimensions: 3cm x 5cm x
0.5cm] or pure aluminum conforming to JIS H4000 [Taishi base material: A 1100 P, dimensions: 5cm x 5cm x
0.2 cm] and heat ray reflective glass [trade name: KLS, dimensions: 5 cm × 5 cm × 0.6 cm]. These adherends were washed with methyl ethyl ketone (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) before filling with the formulation, and wiped with a clean cotton cloth.

The H-type tensile test sample prepared by the above method was subjected to a tensile speed of 50 mm / min in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 65 ± 5% according to the tensile adhesion test method specified in JIS A 5758-1992. Performed under conditions. In the table, cohesive failure (CF), thin layer failure (TCF), and adhesive failure (AF)
Is the rate at which the fracture surface after the tensile test was visually evaluated.

[0132]

Reference Examples 3 and 4 Paraffin-based process oil [Diana Process PS-32, manufactured by Idemitsu Kosan Co., Ltd.] 90 per 100 parts by weight of the polymer obtained in Production Example 2
Parts by weight, heavy calcium carbonate [Shiroishi Calcium Co., Ltd.]
180 parts by weight, manufactured by Shiraishi Kogyo Co., Ltd., trade name: EDS-D10
A] 50 parts by weight, talc [manufactured by Maruo Calcium Co., Ltd., trade name: LMR] 100 parts by weight, antioxidant 1 [manufactured by Ciba Geigy Co., Ltd., trade name: Irganox 1010] 1 part by weight, antioxidant 2 [Sumitomo] 1 part by weight, trade name Sumisorb 400, manufactured by Chemical Co., Ltd., anti-aging agent 3 [Sankyo Co., Ltd.]
Manufactured by Sanshin LS-765], 1 part by weight, light stabilizer [manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sandant NB]
C] 3 parts by weight, photocurable resin [manufactured by Toagosei Co., Ltd., trade name Alonix M400] 3 parts by weight, thixotropic agent [Kusumoto Kasei Co., Ltd., trade name Dispalon # 305]
5 parts by weight, 4 parts by weight of a silane coupling agent γ-isocyanatopropyltriethoxysilane [manufactured by Nippon Unicar Co., Ltd., trade name: Y-9030], and γ-glycidoxypropyltrimethoxysilane [manufactured by Nippon Unicar Co., Ltd. A-187] (2 parts by weight) and kneaded well with a three-paint roll to obtain a base material of Reference Example 3.

As a silanol condensation catalyst, 4 parts by weight of dibutyltin bisacetylacetonate [trade name: U-220, manufactured by Nitto Kasei Co., Ltd.], and sodium sulfate (Na ₂ SO ₄ .10H)
₂ O) 4 parts by weight, paraffin-based process oil [Diana Process PS-32, manufactured by Idemitsu Kosan Co., Ltd.) 10
Parts by weight, heavy calcium carbonate [Maruo Calcium Co., Ltd.
Manufactured by Snow Light SS], 20 parts by weight, carbon black [Mitsubishi Kasei Co., Ltd., trade name: CB # 30]
After manually mixing and kneading 2.5 parts by weight in a disposable cup, using an Excel Auto Homogenizer manufactured by Nippon Seiki Seisaku-sho at a speed of 10,000 rpm and a speed of 10,000 rpm.
The operation of stirring for 3 minutes was performed three times to prepare the curing agent of Reference Example 3.

Further, as Reference Example 4, the base material obtained by adding 4 parts by weight of sodium sulfate (Na ₂ SO ₄ · 10H ₂ O) to the base material of Reference Example 3 was used, and the curing agent of Reference Example 3 without adding sodium sulfate was used. The same test as in Reference Example 3 was used as a curing agent. Each of the above compositions was placed in a sealed glass bottle and placed at 50 ° C.
Was stored in a perfect oven for one month, and the time-dependent changes in adhesion and mechanical properties to various substrates immediately after preparation of the composition and after storage were confirmed by the following test methods. The results are shown in Tables 1 and 2.

A sample for a tensile test was JIS A 5758-1992.
According to the prescribed method for producing a tensile adhesion test specimen, glass,
Alternatively, the aluminum base material is assembled into an H-shape, and the above-mentioned main agent and the curing agent are weighed so as to have a ratio of the total of the main agent component parts by weight and the total of the curing agent component parts by weight, and after sufficiently kneading, the mixture is mixed. After filling, it was cured in an oven. The curing conditions are all 23 ° C. × 7 days + 50 ° C. × 7 days.

The substrate used for the H-type tensile test was JIS A5
Float glass based on 758-1992 [manufactured by Koensha: Designated by the Japan Sealing Material Association, dimensions: 3cm x 5cm x 0.5
cm], or pure aluminum conforming to JIS H4000 [made by Taiyo base material: A 1100 P, dimensions: 5 cm × 5 cm × 0.
2cm], heat ray reflective glass [Product name: KLS, dimensions: 5]
cm × 5 cm × 0.6 cm]. These adherends were washed with methyl ethyl ketone (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) before filling with the formulation, and wiped with a clean cotton cloth.

The H-type tensile test sample prepared by the above method was subjected to a tensile adhesion test method specified in JIS A 5758-1992 in a constant temperature chamber at a temperature of 23 ° C. and a humidity of 65 ± 5%, and a tensile speed of 50 mm / min. Performed under conditions. In the table, cohesive failure (CF), thin layer failure (TCF), and adhesive failure (AF)
Is the rate at which the fracture surface after the tensile test was visually evaluated.

[0138]

[Table 1]

[0139]

[Table 2]

[0140]

Example 3 U-22 which is the silanol catalyst of Example 2
A hardening agent was prepared in the same manner as in Example 2 except that 4 parts by weight of dibutyltin dimethoxide [manufactured by Aldrich Chemical Co., Ltd.] was used instead of 0, and the main agent used in Example 2 was used. The same test as in No. 2 was performed. The results are shown in Tables 3 and 4.

[0141]

Reference Example 5 U-22 which is the silanol catalyst of Reference Example 3
A curing agent was prepared in the same manner as in Reference Example 3 except that 4 parts by weight of dibutyltin dimethoxide [manufactured by Aldrich Chemical Co., Ltd.] was used instead of 0, and the base material used in Reference Example 3 was used. The same test as in No. 3 was performed. The results are shown in Tables 3 and 4.

[0142]

[Table 3]

[0143]

[Table 4]

[0144]

Examples 4 to 7 Paraffin-based process oil [Idemitsu] was added to 100 parts by weight of the silyl group-containing ethylene / propylene / 5-ethylidene-2-norbornene random copolymer rubber (A-1) obtained in Production Example 1. Product name of Kosan Co., Ltd.
Diana Process PS-32] 90 parts by weight, heavy calcium carbonate [manufactured by Shiraishi Calcium Co., Ltd., trade name PO32
0B] 180 parts by weight, colloidal calcium carbonate [Shiraishi Kogyo Co., Ltd., trade name EDS-D10A] 50 parts by weight, talc [Maruo Calcium Co., Ltd. trade name, LMR] 10
0 parts by weight, anti-aging agent 1 [Ciba Geigy K.K., trade name Irganox 1010] 1 part by weight, anti-aging agent 2
1 part by weight of Sumitomo Chemical Co., Ltd., trade name Sumisorb 400, 1 part by weight of antioxidant 3 [manufactured by Sankyo Co., Ltd., trade name of SANOL LS-765], light stabilizer [Sanshin Chemical Industry Co., Ltd.] 3 parts by weight, trade name Sandant NBC], 5 parts by weight of a thixotropic agent [Kusumoto Kasei Co., Ltd., trade name Dispalon # 305], silane coupling agent 1 [Nihon Unicar Co., Ltd., trade name Y- 9030] and 2 parts by weight of a silane coupling agent 2 [manufactured by Nippon Unicar Co., Ltd., trade name: A-187], and kneaded well with a triple paint roll to obtain the main ingredients of Reference Examples 6 to 9.

Also, 4 parts by weight of a silanol condensation catalyst [trade name: U-220, manufactured by Nitto Kasei Co., Ltd.]
₂ SO ₄ .10H ₂ O) 4 parts by weight, paraffinic process oil [manufactured by Idemitsu Kosan Co., Ltd., trade name Diana Process PS-32] 10 parts by weight, heavy calcium carbonate [manufactured by Maruo Calcium Co., Ltd., trade name] Snow Light SS] 20 parts by weight, carbon black [Mitsubishi Kasei Co., Ltd. product name
[CB # 30] 2.5 parts by weight were manually mixed and kneaded in a disposable cup, and the number of revolutions was 10,000 using an Excel Auto Homogenizer manufactured by Nippon Seiki Seisaku-sho, Ltd.
The operation of stirring at 10 rpm for 10 minutes was performed three times to prepare the curing agent of Example 4.

Glauber's salt (Na ₂ SO ₄ .10H) in this curing agent
Instead of ₂ O), hypo as hydrates of metal salts (Na ₂
Example 5 using 6 parts by weight of S ₂ O ₃ .5H ₂ O)
Curing agent, a curing agent of Example 6 to that used 6 parts by weight of magnesium sulfate _{(MgSO 4 · 7H 2 O)} , those using 4 parts by weight of sodium phosphate _{(Na 3 PO 4 · 12H 2} O) The same evaluation as in Example 2 was performed using the same as the curing agent of Example 7. The results are shown in Tables 5 and 6.

[0147]

Reference Examples 6 to 9 Paraffin-based process oil [Diana Process PS-32, trade name, manufactured by Idemitsu Kosan Co., Ltd.]
Parts by weight, heavy calcium carbonate [Shiroishi Calcium Co., Ltd.]
180 parts by weight, manufactured by Shiraishi Kogyo Co., Ltd., trade name: EDS-D10
A] 50 parts by weight, talc [manufactured by Maruo Calcium Co., Ltd., trade name: LMR] 100 parts by weight, antioxidant 1 [manufactured by Ciba Geigy Co., Ltd., trade name: Irganox 1010] 1 part by weight, antioxidant 2 [Sumitomo] 1 part by weight, trade name Sumisorb 400, manufactured by Chemical Co., Ltd., anti-aging agent 3 [Sankyo Co., Ltd.]
Manufactured by Sanshin LS-765], 1 part by weight, light stabilizer [manufactured by Sanshin Chemical Industry Co., Ltd., trade name: Sandant NB]
C] 3 parts by weight, 5 parts by weight of a thixotropic agent [Kusumoto Kasei Co., Ltd. product name, Dispalon # 305], silane coupling agent 1 [Nihon Unicar Co., Ltd. product name, Y-90]
30] and 2 parts by weight of a silane coupling agent 2 [manufactured by Nippon Unicar Co., Ltd., trade name A-187], and kneaded well with a triple paint roll to obtain the main ingredients of Reference Examples 6 to 9.

Further, 4 parts by weight of a silanol condensation catalyst [trade name: U-220, manufactured by Nitto Kasei Co., Ltd.]
₂ SO ₄ .10H ₂ O) 4 parts by weight, paraffinic process oil [manufactured by Idemitsu Kosan Co., Ltd., trade name Diana Process PS-32] 10 parts by weight, heavy calcium carbonate [manufactured by Maruo Calcium Co., Ltd., trade name] Snow Light SS] 20 parts by weight, carbon black [Mitsubishi Kasei Co., Ltd. product name
[CB # 30] 2.5 parts by weight were manually mixed and kneaded in a disposable cup, and the number of revolutions was 10,000 using an Excel Auto Homogenizer manufactured by Nippon Seiki Seisaku-sho, Ltd.
The operation of stirring at 10 rpm for 10 minutes was performed three times to prepare a curing agent of Reference Example 6.

Glauber's salt (Na ₂ SO ₄ .10H) in this curing agent
Instead of ₂ O), hypo as hydrates of metal salts (Na ₂
Reference Example 7 using 6 parts by weight of S ₂ O ₃ .5H ₂ O)
Curing agent, a curing agent of Example 8 that used 6 parts by weight of magnesium sulfate _{(MgSO 4 · 7H 2 O)} , those using 4 parts by weight of sodium phosphate _{(Na 3 PO 4 · 12H 2} O) The same evaluation as in Reference Example 3 was carried out using the curing agent of Reference Example 9. The results are shown in Tables 5 and 6.

The compositions comprising the main agent and the curing agent obtained in Examples 1 to 7 and Reference Examples 1 to 9 were subjected to a curing rate test and a weather resistance test according to the above-mentioned methods. Table 7 shows the results.

[0151]

[Table 5]

[0152]

[Table 6]

[0153]

[Table 7]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/541 C08K 5/57 5/57 C08L 101/10 C08L 101/10 C09D 183/04 C09D 183/04 C09J 183/04 C09J 183/04 F16J 15/14 F16J 15/14 C08K 5/54 (72) Inventor Yoshiharu Kikuchi 3rd Chigusa Coast, Ichihara-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Inventor Arino Mitsuo Nagai, Chitose, Chiba Pref. 3 Mitsuko Nagasaki, Ichihara-shi, Chiba Pref. Mitsui Chemicals Co., Ltd. (72) Inventor Hiroshi Sakaguchi, Yokohama, Kanagawa 1190 Kasama-cho, Sakae-ku, Mitsui Chemical Co., Ltd. (72) Inventor Masaki Sugawara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Pref. Masao Masao 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Kaoru Ueno 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Chemicals (72) Inventor Takashi Abe Yokohama, Kanagawa Prefecture 1190 Kasama-cho, Sakae-ku, Mitsui Chemicals Co., Ltd. AD17 AD18 BB22 BB23 CA11 4J002 BB151 BB201 DD077 DE027 DE147 DE237 DF037 DG047 EX018 EX058 EX068 EX078 EX088 EZ036 FD010 FD020 FD146 FD157 FD208 GH00 GJ00 GQ00 4J038 CB0315 GA12 GA071 JA44 JB39 JC26 JC37 JC38 KA03 KA04 MA09 NA03 NA08 NA11 NA14 NA21 NA23 PA19 PB01 PB02 PB05 PB07 PB09 PC02 PC03 PC06 PC08 4J040 DA031 EK022 EK032 EK042 GA01 GA03 GA04 GA14 GA22 GA24 GA31 HC092 HC12 HC03 HC092 2 HD30 HD42 HD43 JA02 JA13 JB02 KA14 KA16 LA06 LA07 LA08 LA09 MA03 MA04 MA05 MA06 MA08 MA10 NA02 NA05 NA12 NA13 NA15 NA19 PA30 4J100 AA02P AA03Q AA04Q AA15Q AA16Q AA17Q AA19Q AA21Q AS15R AU21 DA31

Claims (24)

[Claims] An unconjugated polyene having at least one structural unit derived from a norbornene compound having a terminal vinyl group represented by the following general formula [I] or [II],
A main agent (I) containing a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) having a hydrolyzable silyl group represented by the following general formula [III] in the molecule, and Silanol condensation catalyst (B)
And a curing agent (II) containing water or a hydrate of a metal salt (C).
Liquid or multi-component curable rubber composition; Wherein n is an integer of 0 to 10, R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. , Embedded image Wherein R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. [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 hydrolyzable group selected from a mercapto group, an alkenyloxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2.]. 2. The curable rubber composition according to claim 1, wherein the silanol condensation catalyst (B) is a tetravalent tin compound. 3. The curable rubber composition according to claim 2, wherein said tetravalent tin compound is a dialkyltin dialkoxide. 4. The curable rubber according to claim 1, wherein the metal salt hydrate (C) is a hydrate of an alkali metal salt or a hydrate of an alkaline earth metal salt. Composition. 5. The curable rubber composition according to claim 1, wherein a silane coupling agent is further compounded in the main agent (I). 6. The silane coupling agent has a hydrolyzable group bonded to a silicon atom, a silicon-containing group capable of crosslinking by forming a siloxane bond, a primary amino group, a secondary amino group, The curable rubber composition according to claim 5, which is a compound having at least one group selected from the group consisting of a tertiary amino group, an epoxy group, an isocyanate group, and an isocyanurate. 7. A main agent (I) containing an organic polymer (D) containing a hydrolyzable silyl group represented by the following general formula [III] and containing substantially no unsaturated double bond in the main chain: And a curing agent (II) containing a silanol condensation catalyst (B) and water or a metal salt hydrate (C).
A two-component or multi-component crosslinkable rubber composition comprising a liquid, which is used for electric / electronic parts, transportation equipment, civil engineering / construction, medical care or leisure use, and is a curable rubber composition. Object; [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 hydrolyzable group selected from a mercapto group, an alkenyloxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2.]. 8. The electric / electronic component is used for heavy electric parts,
Light electrical parts, sealing materials, potting materials, coating materials or adhesives for circuits and substrates of electric and electronic equipment;
8. A material for repairing an electric wire coating; an insulating sealing material for electric wire joint parts; a roll for OA equipment; a vibration absorber; or a gel or capacitor encapsulating material.
3. The rubber composition according to item 1. 9. The rubber composition according to claim 8, 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. 10. The high-voltage transformer with a variable resistance part, wherein the potting material is a transformer high-voltage circuit, a printed circuit board,
The rubber composition according to claim 8, which is used for potting an electric insulating part, a semiconductive part, a conductive part, a solar cell, or a flyback transformer for a television. 11. 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 8, which is used for coating a buffer material for a wire; a semiconductive element; or an optical fiber for optical communication. 12. The rubber composition according to claim 8, wherein the adhesive is used for bonding cathode ray tube wedges, necks, electrically insulating parts, semiconductive parts or conductive parts. 13. The rubber composition according to claim 7, wherein the use of the transport machine is a use of an automobile, a ship, an aircraft, or a railway vehicle. 14. The use of the automobile is as a sealing material for a gasket, an electric component or an oil filter of an automobile engine; a potting material for an igniter HIC or a hybrid IC for an automobile; an automobile body, a window glass for an automobile or an engine control board. 14. The rubber composition according to claim 13, 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. 15. The rubber composition according to claim 13, wherein the use of the ship is a wiring junction box, a sealing material for electric system parts or electric wires; or an adhesive for electric wires or glass. . 16. The civil and architectural uses are associative joints of a commercial building with a glass screen method, joints around a glass between sashes, interior joints in toilets, washrooms or showcases, joints around bathtubs, prefabricated joints. Sealants for building materials used for expansion joints for exterior walls for houses and joints for sizing boards; sealing materials for double-glazed glass; sealants for civil engineering used for road repair; metals, glass,
The rubber composition according to claim 7, which is used for a paint / adhesive for stone, slate, concrete or tile; or an adhesive sheet, a waterproof sheet or a vibration-proof sheet. 17. The rubber composition according to claim 7, wherein the medical use is a sealing material for a rubber stopper for medicine, a syringe gasket, or a rubber stopper for a reduced-pressure blood vessel. 18. The rubber composition according to claim 7, 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. object. 19. A main agent (I) containing an organic polymer (C) containing a hydrolyzable silyl group represented by the following general formula [III] and having substantially no unsaturated double bond in the main chain. ,
And a curing agent (II) containing a silanol condensation catalyst (B) and water or a metal salt hydrate (C), a two-part or multi-part crosslinkable rubber composition comprising at least two parts. A sealing material characterized by the following: [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 hydrolyzable group selected from a mercapto group, an alkenyloxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2.]. 20. A main agent (I) containing an organic polymer (C) containing a hydrolyzable silyl group represented by the following general formula [III] and having substantially no unsaturated double bond in the main chain. ,
And a curing agent (II) containing a silanol condensation catalyst (B) and water or a metal salt hydrate (C), a two-part or multi-part crosslinkable rubber composition comprising at least two parts. A potting material characterized by: [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 hydrolyzable group selected from a mercapto group, an alkenyloxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2.]. 21. A main agent (I) containing an organic polymer (C) containing a hydrolyzable silyl group represented by the following general formula [III] and containing substantially no unsaturated double bond in the main chain. ,
And a curing agent (II) containing a silanol condensation catalyst (B) and water or a metal salt hydrate (C), a two-part or multi-part crosslinkable rubber composition comprising at least two parts. A coating material characterized by becoming: [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 hydrolyzable group selected from a mercapto group, an alkenyloxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2.]. 22. A main agent (I) containing an organic polymer (C) containing a hydrolyzable silyl group represented by the following general formula [III] and having substantially no unsaturated double bond in the main chain. ,
And a curing agent (II) containing a silanol condensation catalyst (B) and water or a metal salt hydrate (C), a two-part or multi-part crosslinkable rubber composition comprising at least two parts. An adhesive characterized by becoming; [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 hydrolyzable group selected from a mercapto group, an alkenyloxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2.]. 23. A main agent (I) containing an organic polymer (C) containing a hydrolyzable silyl group represented by the following general formula [III] and containing substantially no unsaturated double bond in the main chain. ,
And a curing agent (II) containing a silanol condensation catalyst (B) and water or a metal salt hydrate (C), a two-part or multi-part crosslinkable rubber composition comprising at least two parts. A foam material composition characterized by the following: [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 hydrolyzable group selected from a mercapto group, an alkenyloxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2.]. 24. Condensation of the composition according to claim 23,
The foaming material composition according to claim 23, wherein a gas generated during the condensation is used as a foaming agent.