JP2002037952A - Curable composition and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which gives cured products having excellent weather resistance at high curing speeds and is suitably used as an adhesive, a sealant, and so on. SOLUTION: This curable composition characterized by comprising (a) a silyl group-containing ethylene/α-olefin/non-conjugated polyene random copolymer rubber (A) which has constituent units derived from a terminal vinyl group- containing norbornene compound of non-conjugated polyene and which contains specified hydrolysable silyl groups in the molecule, (b) a compound (B) having a silonol group in the molecule and (or) a compound whose hydrolysable silicone group can react with water to produce a compound having one silanol group in the molecule, (c) a compound (C) which has an amino group and a group containing silicon having two hydrolysable groups bound to thereto, and (d) a compound (D) which has an amino group and a group containing silicon bound to three hydrolysable groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a curable composition and its use, and more particularly to a silicon compound having a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom, which can be crosslinked by forming a siloxane bond. The present invention relates to a curable composition containing an α-olefin copolymer rubber having a containing group.

[0002]

2. Description of the Related Art An oxyalkylene having a hydroxyl group and / or a hydrolyzable group bonded to a silicon atom and having a silicon-containing group capable of being crosslinked by forming a siloxane bond (hereinafter also referred to as a reactive silicon group). The system polymer is
It is disclosed in JP-A-52-73998 and the like, and a typical example is a general formula:

[0003]

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(Wherein X ″ is a hydrolyzable group such as a methoxy group.) An oxyalkylene-based polymer having a reactive silicon group is formed at room temperature like a room-temperature-curable silicone rubber. It cures by forming siloxane bonds (Si-O-Si) between polymers under the action of moisture in the air, etc. to give a rubber-like cured product, which has excellent elongation properties, strength, adhesion, etc. It is used for applications such as sealants and adhesives.

Various properties are required for rubber-like cured products used for sealants and the like, and tensile properties and adhesion to adherends are important properties. The adhesive properties are properties such as modulus, elongation, and breaking strength, but low modulus and high elongation, which are characteristics of rubber, are often required.
The adhesiveness is a property such as an adhesive strength to an adherend and weather resistance of the adhesive strength. However, high adhesive strength and weather resistance with high adhesive strength are required. In particular, when used as a building sealant, it is often used for a transparent material such as glass, and weather resistance of adhesive strength, particularly weather resistance during light irradiation, is an important property.

As disclosed in JP-A-61-34066, a composition containing an oxyalkylene polymer having a reactive silicon group that gives a cured product having a low modulus, as disclosed in JP-A-61-34066. A compound having one silanol group in the molecule and / or a compound capable of forming a compound having one silanol group in the molecule by reacting a hydrolyzable silicon group in the molecule with water (hereinafter referred to as monovalent silanol) (Also referred to as a system compound).

Oxyalkyl having a reactive silicon group
In order to improve the adhesion of the cured product of the len-based polymer, γ-
Aminopropyltrimethoxysilane (H_TwoNCH_TwoCH_TwoCH_TwoSi (OC
H_Three) _Three) And γ-aminopropylmethyldimethoxysilane
(H_TwoNCH_TwoCH_TwoCH_TwoSi (CH_Three) (OCH_Three)_TwoHydrolysable like)
Compound having a silicon atom and an amino group to which a group is bonded
It has been proposed in JP-A-57-182350 to use
I have.

However, a composition using a compound having a silicon atom to which three hydrolyzable groups are bonded, such as γ-aminopropyltrimethoxysilane, has a high cured product modulus and a monovalent property. There is a disadvantage that the effect of the silanol-based compound is reduced. Also, γ-
A composition using a compound having a silicon atom to which two hydrolyzable groups are bonded, such as aminopropylmethyldimethoxysilane, has a relatively low modulus of the cured product, but has a low adhesive strength. There is a disadvantage that the weather resistance is insufficient.

Further, Japanese Patent Application Laid-Open No. 2-117555 discloses that two hydrolyzable groups are bonded to a composition comprising an oxyalkylene polymer having a reactive silicon group and a monovalent silanol compound. Curable composition containing a compound having a silicon atom and an amino group and a small amount of a compound having a silicon atom and an amino group to which three hydrolyzable groups are bonded have modulus properties and adhesive strength to adherends It is proposed that the weather resistance of the adhesive strength is improved. However, the weather resistance of the obtained cured product was not sufficient, and there was room for improvement.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a curable composition which can be suitably used as an adhesive or a sealing material, which gives a cured product having a high curing rate and excellent weather resistance. Challenges.

[0011]

The present invention for solving the above-mentioned problems is based on (a) a non-conjugated polyene derived from at least one kind of norbornene compound having a terminal vinyl group represented by the following general formula [I] or [II]. Having a structural unit
And a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) containing a hydrolyzable silyl group represented by the following general formula [III] in the molecule:

[0012]

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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],

[0014]

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

[0016]

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[Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group, a ketoximate group, A hydrolyzable group selected from an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. And an amino group-substituted silane compound (X).

The curable composition of the present invention comprises (a) the above-mentioned silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A), and (b) one silanol group in the molecule. A compound (B) capable of producing a compound having one silanol group in the molecule by reacting a compound and / or a hydrolyzable silicon group in the molecule with water, and the amino group-substituted silane compound ( (C) compounds (C) and (d) each having (c) a silicon-containing group to which two hydrolyzable groups are bonded and an amino group as X)
It is preferable that the compound contains a silicon-containing group to which two hydrolyzable groups are bonded and a compound (D) having an amino group.

The present invention for solving the above problems further comprises:
(A) an organic polymer containing a hydrolyzable silyl group represented by the following general formula [III] and containing substantially no unsaturated double bond in the main chain;

[0020]

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[Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group, a ketoximate group, A hydrolyzable group selected from an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. And a curable composition containing an amino group-substituted silane compound (X), characterized in that it is used for electric / electronic parts, transport, civil engineering / architecture, medical or leisure applications. This is a curable composition.

The curable composition also contains (a) a hydrolyzable silyl group represented by the above general formula [III],
An organic polymer substantially free of unsaturated double bonds in the main chain,
(B) a compound having one silanol group in the molecule and / or a compound capable of producing a compound having one silanol group in the molecule by reacting a hydrolyzable silicon group in the molecule with water ( B) and (c) the amino-substituted silane-based compound (X), a compound (C) having a silicon-containing group to which two hydrolyzable groups are bonded and an amino group and (d) 3 (D) having a silicon-containing group to which two hydrolyzable groups are bonded and an amino group
Is desirable.

The present invention for solving the above-mentioned problems further comprises:
(A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula [III] and having substantially no unsaturated double bond in the main chain, and an amino-substituted silane compound (X)
A sealing material comprising a curable composition containing The present invention which solves the above-mentioned problems,
(A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula [III] and having substantially no unsaturated double bond in the main chain, and an amino-substituted silane compound (X)
A potting material comprising a curable composition containing:

The present invention for solving the above-mentioned problems further comprises:
(A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula [III] and having substantially no unsaturated double bond in the main chain, and an amino-substituted silane compound (X)
A coating material comprising a curable composition containing: The present invention for solving the above-mentioned problems further comprises (a) an organic polymer containing a hydrolyzable silyl group represented by the above general formula [III] and containing substantially no unsaturated double bond in the main chain; And an curable composition containing an amino group-substituted silane compound (X).

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. [Silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A)] The silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) used in the present invention is as follows: 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.

[0026]

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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. Yes, for example, methyl, ethyl, propyl,
Alkyl groups such as butyl group, hexyl group and cyclohexyl group, aryl groups such as phenyl group and tolyl group, and groups in which part or all of the hydrogen atoms bonded to these carbon atoms have been substituted with halogen atoms such as fluorine atoms. No.

X represents a hydride group (—H), a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group (—CONH ₂ ), an acid amide group, an aminooxy group ( -O
NH ₂ ), a thioalkoxy group, or an amino group (—NH
₂ ). Specific examples of a halogen group, an alkoxyl group, an acyloxy group, a ketoximate group, an acid amide group, and a thioalkoxy group include the same groups as those of 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.

Examples of such α-olefins having 3 to 20 carbon atoms include propylene, 1-butene,
4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 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 may 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.

[0032]

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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 .

[0035]

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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-2
-In addition to 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, 4,5-dimethyl-1,4-hexadiene, 7-methyl
Chain non-conjugated dienes such as -1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-
Cyclic non-conjugated dienes such as methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene and dicyclopentadiene; 2,3 And trienes such as -diisopropylidene-5-norbornene, 2-ethylidene-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 properties and rubber elasticity and can provide a crosslinked rubber molded article excellent in cold resistance and workability 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 degradation 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 d
1 / g, more preferably 0.05 to 0.7 dl / g,
Particularly preferably, it is preferably 0.1 to 0.5 dl / g.

When the intrinsic viscosity [η] is within the above range, a rubber composition having excellent fluidity and capable of providing a crosslinked rubber molded article having excellent strength properties and compression set resistance can be obtained. (Iv) Molecular weight distribution (Mw / Mn) 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 can be 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 / cm
^2. Under the condition of the molar ratio of the non-conjugated polyene and ethylene supplied (non-conjugated polyene / ethylene) of 0.01 to 0.2,
Ethylene, an α-olefin having 3 to 20 carbon atoms,
It can be obtained by random copolymerization with a norbornene compound having a terminal vinyl group represented by the general formula [I] or [II]. The copolymerization is preferably carried out in a hydrocarbon medium. (H) a soluble vanadium compound represented by VO (OR) _n X _3-n (where R is a hydrocarbon group, X is a halogen atom, and n is an integer of 0 or 1 to 3), Or a vanadium compound represented by VX ₄ (X is a halogen atom).

The soluble vanadium compound (H) is a component which is soluble in a hydrocarbon medium of a polymerization reaction system, and specifically, has the general formula VO (OR) _{a Xb} or V (OR) _c X _d
(Where R is a hydrocarbon group, 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,
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, for example, JP-A-9-4058
No. 6 may be used. Silicon Compound The silicon compound used in the present invention has the following general formula [IV]
Is represented by

[0048]

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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, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group, a ketoximate group, an amide group (—CONH ₂ ), an acid amide group, an aminooxy group ( -O
NH ₂ ), a thioalkoxy group, or an amino group (—NH
₂ ). 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 ketoxime group include an acetoxymate group, a dimethyl ketoxime group, a diethyl ketoxime, and a cyclohexyl ketoxmate group. Examples of the amide group include a dimethylamide group, a diethylamide group, a dipropylamide group, a dibutylamide group, and a diphenylamide group.

Examples of the acid amide group include a carboxylic acid amide group, a maleic acid amide group, an acrylic acid amide group,
And itaconic acid amide groups. Examples of the thioalkoxy group include a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thioisopropoxy group, a sec-thiobutoxy group, a tert-thiobutoxy group, a thiopentyloxy group, a thiohexyloxy group, and a thiophenoxy group. .

Examples of the amino group include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group and a diphenylamino group. Among these, alkoxyl groups, especially those having 1 to 4 carbon atoms.
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, butyldiethoxysilane, phenyldimethoxysilane; triacetoxysilane, methyldimethoxysilane Acyloxysilanes such as acetoxysilane and phenyldiacetoxysilane; ketoxies such as tris (acetoxymate) silane, bis (dimethylketoxime) methylsilane, bis (methylethylketoxime) methylsilane, bis (cyclohexylketoxime) methylsilane Mate silanes; aminoxy silane,
Examples include aminooxysilanes such as triaminoxysilane; aminosilanes such as methyldiaminosilane and triaminosilane. Of these, alkoxysilanes are particularly desirable.

The silicon compound represented by the 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 10,000 ppm as a metal unit with respect to the reactant (ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A ₀ ), Preferably 1 to 100
0 ppm, particularly preferably 20 to 200 ppm.
The preferred temperature for this hydrosilation reaction is between 30 and
The temperature is 180 ° C, preferably 60 to 150 ° C. In addition, this hydrosilylation reaction can be performed under pressure, if necessary. The reaction time is about 10 seconds to 10 hours.

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.

[0058]

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[0059]

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

[0061]

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(Wherein, 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. In the present invention, the use of the hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) having such a structure is mainly attributable to curing speed and weather resistance. Demonstrates excellent properties.

[Monovalent Silanol Compound (B)] The composition of the present invention may contain, as necessary, a compound having one silanol group in the molecule and / or a compound having one silanol group in the molecule by reacting with water. A compound capable of forming a compound having two silanol groups (monovalent silanol compound) (B) is used. By using this component (B), an effect of reducing the modulus of the cured product of the hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) can be expected. This component can be easily obtained, and the above effect can be obtained simply by adding it to the ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) containing a hydrolyzable silyl group. It has features.

The compound having one silanol group in the molecule, which is one of the monovalent silanol compounds, can be used without any particular limitation as long as it is a compound having one SiOH group in the molecule. As specific examples of the compound,
For example, (CH ₃ ) ₃ SiOH, (CH ₃ CH ₂ ) ₃ SiOH, (CH ₃ CH ₂ CH ₂ ) ₃ S
iOH, (C ₆ H ₅ ) ₃ SiOH,

[0065]

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A general formula such as: (R ³ ) ₃ SiOH (wherein R ³
Are the same or different C1-C20 substituted or unsubstituted alkyl or aryl groups),

[0067]

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A cyclic polysiloxane compound containing a silanol group such as

[0069]

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(Wherein, R ³ is the same or different and has 1 to 1 carbon atoms)
A chain polysiloxane compound containing a silanol group such as 20 substituted or unsubstituted alkyl groups or aryl groups, and n is 0 or an integer of 1 to 40. Among these compounds, the higher the SiOH group content, the greater the effect at the same addition amount. From this point, (C
H ₃ ) ₃ SiOH and (CH ₃ CH ₂ ) ₃ SiOH are preferred. From the viewpoint of ease of handling and stability in air, (C ₆ H ₅ ) ₃ SiO
H is preferred.

A compound capable of reacting with water, which is one of monovalent silanol compounds, to form a compound having one silanol group in a molecule is known as a so-called silylating agent.

[0072]

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And the like, which can be preferably used.
In view of the high SiOH content of the hydrolysis product

[0074]

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Is particularly preferred. These compounds are effective for improving the tensile properties of the cured product, that is, for reducing the modulus and elongation, because these compounds are hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymers. By reacting with the hydrolyzable silyl groups in the rubber (A) and capping, the number of cross-linking points in the cured polymer decreases, the molecular weight between cross-linking points increases, and as a result, low modulus and high elongation can be achieved. It is considered to be achieved.

The amount of the monovalent silanol compound to be added is generally 0.1 to 20 parts with respect to 100 parts of a hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). , More preferably 0.5 to
10 parts, but hydrolyzable silyl group-containing ethylene α
-The addition amount can also be determined by calculating the silanol equivalent (SiOH) with respect to the hydrolyzable silyl group contained in the olefin / non-conjugated polyene random copolymer rubber (A). Usually, the equivalent of the silanol group may be 0.1 to 0.9 times the hydrolyzable silyl group. However, the number of hydrolyzable silyl groups remaining without being completely capped by the compound is at least within the molecule of the hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). Preferably, one remains. It is possible to use more than 0.9 times the equivalent of a silanol group, but this is not advantageous in terms of economy.

[Amino group-substituted silane compound (X)] The curable composition of the present invention contains the above-mentioned hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A) And an amino group-substituted silane compound (X) is compounded. As the amino group-substituted silane compound (X), various compounds can be used alone or in combination of two or more. The bifunctional aminosilane compound (C) and the trifunctional aminosilane compound (D) described in detail below are used. Are preferably used in combination.

[Bifunctional aminosilane compound (C)] A compound having an amino group and a silicon-containing group to which two hydrolyzable groups are bonded (hereinafter referred to as a bifunctional aminosilane compound (C)) used in the present invention. Representative examples of the silicon-containing group to which the hydrolyzable group in ()) is bonded are represented by the general formula:

[0079]

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(Wherein R ² is a monovalent organic group having 1 to 40 carbon atoms, and X ′ is a hydrolyzable group). Examples of the hydrolyzable group include a halogen atom, a hydrogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. An alkoxyl group such as a methoxy group and an ethoxy group is preferred in view of mild hydrolysis. As the amino group, a —NH ₂ group or a substituted amino group in which a hydrogen atom of the —NH ₂ group is substituted with another group can be used. Representative examples of such amino groups have the general formula: -NR ₂ ⁴ (wherein, R ⁴ is a substituted or unsubstituted hydrocarbon group hydrogen atom or 1 to 30 carbon atoms, optionally substituted by one or more identical Or a group represented by

Specific examples of the bifunctional aminosilane compound (C) include H ₂ NCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ and H ₂ NCH ₂ CH ₂ NHC
H ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , (CH ₃ ) NHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OC
_{H 3) 2, (C 2} H 5) NHCH 2 CH 2 NHCH 2 CH 2 CH 2 Si (CH 3) (OCH 3) 2, H 2 N
CH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCOCH ₃ ) ₂ , H ₂ NCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (ON =
_{C (CH 3) (C 2} H 5)) 2, H 2 NCH 2 CH 2 CH 2 Si (CH 3) (OC (CH 3) = CH 2) 2
And the like.

The addition amount of the bifunctional aminosilane compound (C) is preferably 0.1 to 20 parts per 100 parts of the hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). Parts, more preferably 0.5
~ 10 parts. It is not preferable that the amount of the bifunctional aminosilane added is too large relative to the monovalent silanol compound. The weight ratio of the monovalent silanol compound / bifunctional aminosilane is preferably from 1 / 0.01 to 1/5, more preferably from 1 / 0.05 to 1/2.

[Trifunctional Aminosilane Compound (D)] In the compound of the present invention, a compound containing a silicon-containing group to which three hydrolyzable groups are bonded and an amino group (hereinafter referred to as a trifunctional aminosilane compound) is used. A typical example of a silicon-containing group to which a decomposable group is bonded is a compound represented by the general formula: —SiX ₃
(Wherein, X represents a hydrolyzable group). As the amino group, the same groups as described above can be used. Specific examples of the trifunctional aminosilane compound (D) include H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si
(OCH ₃ ) ₃ , (CH ₃ ) NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , (C ₂ H ₅ ) NHCH ₂ CH ₂
NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ CH ₂ Si (OCOCH ₃ ) ₃ , H ₂ N
CH ₂ CH ₂ CH ₂ Si (ON = C (CH ₃ ) (C ₂ H ₅ )) ₃ , H ₂ NCH ₂ CH ₂ CH ₂ Si (OC (C
H ₃ ) = CH ₂ ) _{3 and the} like.

The addition amount of the trifunctional aminosilane compound (D) is preferably 0.01 to 5 parts per 100 parts of the hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). Parts, more preferably 0.
05 to 3 parts. If the addition amount of the trifunctional aminosilane compound is too large, the modulus of the cured product increases.
The trivalent silanol-based compound / functional aminosilane compound is preferably in a weight ratio of 1 / 0.01 to 1 / 0.75, and 1 / 0.02 to 1/0.
More preferably, it is 5.

[Other Formulations] The composition of the present invention includes:
If necessary, a curing accelerator, a plasticizer, a filler, and other additives may be added for use. Examples of the curing accelerator that can be used in the present invention include organic tin compounds, acid phosphates, reactants of acid phosphates with amines, saturated or unsaturated polycarboxylic acids or acid anhydrides thereof, and organic titanates. And the like. Specific examples of the organotin compound include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, tin octylate, dibutyltin methoxide, and the like.

The acidic phosphate ester is

[0087]

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A phosphate ester containing a moiety,
For example

[0089]

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(Wherein, d is 1 or 2, and R ⁵ is an organic group).

[0091]

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[0092]

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And the like. Further, as the organic titanate compound, for example, tetrabutyl titanate,
Examples include titanates such as tetraisopropyl titanate and triethanolamine titanate. When the curing accelerator is used, it is preferably used in an amount of 0.1 to 10 parts with respect to 100 parts of the hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). .

As a plasticizer that can be used in the present invention, a low-molecular plasticizer such as dioctyl phthalate, a high-molecular plasticizer, or a high-viscosity plasticizer can be used. Specific examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate; and non-aromatics such as dioctyl adipate and dioctyl sebacate. Group 2 dibasic acid esters; Polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; Phosphate esters such as tricrene diphosphate and tributyl phosphate; Paraffin chlorides; Alkyl diphenyl, polybutene, hydrogenated polybutene , Ethylene-α-olefin oligomer, α-
Methylstyrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylene triphenyl,
Liquid polybutadiene, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, atactic polypropylene, partially hydrogenated terphenyl and other hydrocarbon-based oils, etc., can be used alone or as a mixture of two or more. it can. These plasticizers can also be blended during the production of the polymer.

Among them, hydrocarbon compounds having no unsaturated group (specifically, hydrogenated polybutene, hydrogenated liquid polybutadiene, paraffin oil, naphthenic oil, atactic polypropylene, etc.) are the compounds of the present invention. It is preferable because it has good compatibility with various components blended into the composition, has little effect on the curing speed of the composition, and has good weather resistance and is inexpensive.

These plasticizers may be used in place of the solvent for the purpose of adjusting the reaction temperature and adjusting the viscosity of the reaction system when introducing the reactive silicon group into the saturated hydrocarbon polymer.
When a plasticizer is used, it is preferably used in an amount of from 1 to 400 parts, more preferably from 1 to 150 parts, per 100 parts of the hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber (A). Parts, more preferably 10-1
20 parts, particularly preferably 20 to 100 parts.

Specific examples of the filler include wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, clay, fumed silica, sedimentation Examples include silica, anhydrous silicic acid, carbon black, calcium carbonate, clay, kaolin, talc, titanium oxide, magnesium carbonate, quartz powder, glass beads, aluminum fine powder, flint powder, zinc powder, and the like. Of these fillers,
Thixotropic fillers such as precipitated silica, fumed silica, and carbon black, calcium carbonate, titanium oxide, and talc are preferred. These fillers may be used alone or in combination of two or more.

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

Examples of the radical inhibitor include 2,2
-Methylene-bis (4-methyl-6-t-butylphenol), tetrakis [methylene-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] a phenolic radical inhibitor such as methane;
-Naphthylamine, α-naphthylamine, N, N'-sec-
Butyl-p-phenylenediamine, phenothiazine, N,
And amine radical inhibitors such as N'-diphenyl-p-phenylenediamine.

As the ultraviolet absorber, for example, 2- (2 ′)
-Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4
-Piperidine) sebacate and the like. The composition of the present invention thus obtained is usefully used as an adhesive, a pressure-sensitive adhesive, a paint, a coating film waterproofing agent, a sealant composition, a molding material, a casting rubber material, a foam material, and the like. Can be.

For example, when applied as a building sealing agent, usually 10 to 300 parts of an inorganic filler such as calcium carbonate, talc or kaolin is added to the composition used in the present invention.
If necessary, add an appropriate amount of an antioxidant such as a pigment such as titanium oxide or carbon black, an ultraviolet absorber, or a radical chain inhibitor, and then knead the mixture uniformly using a kneader or paint roll. It is cured by exposure to the moisture in the air, and a rubber elastic body having good properties is obtained.

[Curable composition and its use] A curable composition containing a hydrolyzable silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber as described above in detail as the component (A). And (a) containing a hydrolyzable silyl group represented by the following general formula [III] and containing substantially unsaturated double bonds in the main chain. No organic polymer,

[0103]

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[Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group, a ketoximate group, A hydrolyzable group selected from an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. ] And an amino group-substituted silane compound (X), and the curable composition is preferably used in electric / electronic parts, transportation equipment, civil engineering / architecture, medical treatment or recreational use. The composition is an acidic composition.

As described above, this curable composition includes (a) a hydrolyzable silyl group represented by the above general formula [III] and a substantially unsaturated double bond in the main chain. (B) a compound having one silanol group in the molecule and / or a hydrolyzable silicon group in the molecule reacting with water to have one silanol group in the molecule A compound (B) capable of forming a compound, and (c) a compound having a silicon-containing group to which two hydrolyzable groups are bonded and an amino group as the amino group-substituted silane compound (X) ( It is desirable to have a composition comprising C) and (d) a compound (D) having a silicon-containing group to which three hydrolyzable groups are bonded and an amino group.

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

[0110] Examples of the above-mentioned medical uses include a rubber stopper for medicine, a syringe gasket, and a rubber stopper for a reduced-pressure blood vessel. 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.

Further, the composition according to the present invention can be used for electric / electronic parts, transport equipment, civil engineering construction, leisure and the like.
It can be suitably used as a sealing material (sealing material), a potting material, a coating material, and an adhesive. That is, the present invention provides (a) an organic polymer containing a hydrolyzable silyl group represented by the above general formula [III] and having substantially no unsaturated double bond in the main chain; A sealing material comprising a curable composition containing a substituted silane compound (X).

The present invention also relates to (a) the above-mentioned general formula [III]
And a curable composition containing the amino group-substituted silane compound (X), which contains a hydrolyzable silyl group represented by the formula (1), and does not substantially contain an unsaturated double bond in the main chain. It is a potting material characterized by becoming.
The present invention further provides (a) an organic polymer containing a hydrolyzable silyl group represented by the above general formula [III] and having substantially no unsaturated double bond in the main chain; A coating material comprising a curable composition containing a silane compound (X).

The present invention further relates to (a) the above-mentioned general formula [III]
And a curable composition containing the amino group-substituted silane compound (X), which contains a hydrolyzable silyl group represented by the formula (1), and does not substantially contain an unsaturated double bond in the main chain. It is an adhesive characterized by becoming. As described above, in these sealing materials, potting materials, coating materials and adhesives, (a) the main chain containing the hydrolyzable silyl group represented by the general formula [III] is substantially contained. An organic polymer containing no unsaturated double bond,
(B) a compound having one silanol group in the molecule and / or a compound capable of producing a compound having one silanol group in the molecule by reacting a hydrolyzable silicon group in the molecule with water ( B) and (c) the amino-substituted silane compound (X), a compound (C) having a silicon-containing group to which two hydrolyzable groups are bonded and an amino group, and (d) It is desirable to have a composition comprising a compound (D) having a silicon-containing group to which three hydrolyzable groups are bonded and an amino group.

[0114]

The composition of the present invention has a high curing rate, keeps the modulus of the cured product low, and can greatly improve both the adhesive strength and the weather resistance.

[0115]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The composition of the copolymer rubber used in the examples and comparative examples,
Iodine value, intrinsic viscosity [η], molecular weight distribution (Mw / M
n), the effective network chain density (ν) was measured or obtained 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.

[0116]

[Production Example] [Silyl group-containing ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1)
Production of Ternary Copolymerization of Ethylene, Propylene, and 5-Vinyl-2-norbornene Continuously Using a 100 L Stainless Steel Polymerizer (Agitating Rotation Speed = 250 rpm) Equipped with Stirring Blades Done. 60 liters of hexane and 2.5 parts of ethylene per hour were added to the liquid phase from the side of the polymerization vessel.
kg, 4.0 kg of propylene, 380 g of 5-vinyl-2-norbornene, 700 liters of hydrogen, 45 mmol of VO (OEt) ₂ Cl as a catalyst, A
l (Et) _1.5 Cl _1.5 was fed continuously at a rate of 315 mmol.

When the copolymerization reaction was carried out under the conditions described above, an ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (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%,
The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.2
dl / g and an iodine value (IV) of 10 (g / 100 g)
And Mw / Mn was 15. To 100 parts by weight of the ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A ₀ -1) obtained as described above, 0.3 part by weight of a 2% chloroplatinic acid solution in toluene was added. , 1.5 parts by weight of methyldimethoxysilane,
The reaction was performed at 20 ° C. for 2 hours. After the reaction, excess methyldimethoxysilane and the solvent (toluene) were distilled off, and a dimethoxymethylsilyl group (—Si (CH ₃ ) (OCH ₃ )) was obtained.
₂ ) An ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) containing 101.5
Parts by weight were obtained.

[0119]

EXAMPLES 1 TO 8 AND REFERENCE EXAMPLE 1 100 g of the silyl group-containing ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A-1) obtained in the production example was mixed with calcium carbonate (F) as a filler. Shiraishi Industry Co., Ltd., trade name CCR) 1
20g, titanium dioxide (R820, manufactured by Ishihara Sangyo Co., Ltd.) 2
0 g, 2 g of dibutyltin diacetylacetonate (trade name: U-220, manufactured by Nitto Kasei Co., Ltd.) as a curing accelerator, paraffin oil (Diana Process Oil P) as a plasticizer
W-380, manufactured by Idemitsu Kosan Co., Ltd.) (Examples 1 to 8 and Reference Example 1) 50 g of monovalent silanol compound in Table 1
2g and the trifunctional aminosilane compound and the bifunctional aminosilane compound as N- (β
-Aminoethyl) -γ-aminopropyltrimethoxysilane (H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ) and N- (β
-Aminoethyl) -γ-aminopropylmethyldimethoxysilane (NH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ) in an amount shown in Table 1 and a three paint roll. After sufficiently kneading and mixing, an H-shaped test piece was prepared according to JIS A 5758, and the tensile properties, adhesive strength, and weather resistance of the adhesive strength at the time of light irradiation (weather resistance adhesive property) were examined. Further, the curing speed and weather resistance (ozone deterioration test) were also examined. Table 1 shows the obtained results. The test method is as follows. (Tensile properties) H-type test piece (substrate,
Anodized aluminum) at 14 ℃ at 23 ℃ and 60% humidity.
After curing for 30 days at 30 ° C,
The tensile test was performed at a speed of minutes. (Adhesive strength) The rupture state of the test piece ruptured by the above tensile test was observed. If the cured product itself breaks (cohesive failure, CF), the adhesion strength to the adherend is large, and if the peeling occurs on the adhesion surface between the adherend and the cured product (bond failure, AF),
Indicates that the adhesive strength is low. (Weather resistance) Prepare H-type test piece (substrate glass) according to JIS A 5758, and irradiate for 480 hours with Sunshine Weatherometer (WEL-3-HC type, manufactured by Suga Test Instruments Co., Ltd.) After the accelerated exposure, a tensile test was performed by an autograph (IS-5000, manufactured by Shimadzu Corporation). (Curing speed test) A curable composition was molded (20 × 80
× 5 mm) and cured for 24 hours at 23 ° C. and 50% relative humidity.

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 is more than 1 mm, ○, 0.5 to 1 mm
The evaluation of the curing rate was represented by Δ when the value was less than 0, and × when the value was less than 0.5 mm. (Weather resistance test) According to JIS B-7753, an accelerated weather resistance test was performed under the following conditions. Sunshine Carbon Arc Weatherometer Irradiation / Rain Cycle 120min Irradiation / 18min Rain Black Panel Temperature 63 ℃ ± 2 ℃, Tank Temperature: 40 ℃ ± 2 ℃ Irradiation Time: 500 hours After this test, cracks with the naked eye ◎: No melting part was observed, 認 め: Cracking or melting part was slightly observed, △: Cracking or melting part was recognized, and △: Cracking or melting part was extremely large. Then, the evaluation of the weather resistance was expressed as x.

[0121]

[Table 1]

Table 2 shows the results of comprehensive evaluation of Examples 1 to 8 and Reference Example 1. In the table, ○ indicates good characteristics, X indicates unfavorable characteristics, and △ indicates intermediate characteristics.

[0123]

[Table 2]

[0124]

[Comparative Production Example] Polyoxypropylene-based polymer having an average molecular weight of about 8000 with allyl ether groups introduced at 97% of all terminals
800 g was placed in a pressure-resistant reaction vessel equipped with a stirrer, and 19 g of methyldimethoxysilane was added. Then, a chloroplatinic acid catalyst solution (H ₂ PtC
l ₆ · 6H and the ₂ O in 8.9g of isopropyl alcohol 18ml and the solution was dissolved in tetrahydrofuran 160 ml) 0.34 ml for 6 hours at 80 ° C. After the addition of. When the amount of the remaining silicon hydride groups in the reaction solution was quantified by 1R spectral analysis, almost no remaining silicon hydride groups remained. When the reactive silicon group was quantified by the NMR method,

[0125]

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Thus, a polyoxypropylene-based polymer (CA-1) having about 1.7 molecules per molecule was obtained.

[0127]

Reference Examples 2 to 10 Silyl group-containing ethylene / propylene / 5-vinyl-2-norbornene random copolymer rubber (A
-1), the polymer synthesized in Comparative Production Example (CA-
1) and a paraffinic oil (Diana Process Oil PW-380, Idemitsu Kosan Co., Ltd.) as a plasticizer
Allyl ether type Mn = 5200, M
w / Mn = 1.6 oxypropylene polymer (Reference Example 2)
To 3, 5 to 10) or (2-ethylhexyl) phthalate (Reference Example 4) manufactured by Daihachi Chemical Co., Ltd., except that a curable composition was prepared in the same manner as in Examples 1 to 8 and Reference Example 1. Then, its characteristics were evaluated. Table 3 shows the obtained results.

[0128]

[Table 3]

Table 4 shows the results of comprehensive evaluation of Reference Examples 2 to 10.
Shown in In the table, ○ indicates good characteristics, X indicates unfavorable characteristics, and △ indicates intermediate characteristics.

[0130]

[Table 4]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/04 C09J 183/04 4J100 C09J 183/04 C09K 3/10 G C09K 3/10 Z F16J 15/10 XF16J 15/10 15/14 C 15/14 C08K 5/54 (72) Inventor Yoshiharu Kikuchi 3rd Chigusa Beach, Ichihara-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Inventor Yasuyoshi Arino Big Chiba 3 Mitsui Chemicals, Ichihara-shi, Mitsui Chemicals Co., Ltd. (72) Inventor Mitsuko Nagai 3 Chikusa-kaigan, Ichihara-shi, Chiba Mitsui Chemicals, Inc. (72) 1190 No. Mitsui Chemicals Co., Ltd. (72) Inventor Masaki Sugawara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture 1190 Kasama-cho, Sakae-ku, Yokohama Mitsui Chemical Co., Ltd. (72) Inventor Kaoru Kaoru Ueno 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Takashi Abe Kasama-cho, Sakae-ku, Yokohama 1190 Mitsui Chemicals Co., Ltd. (72) Michio Sekine Inventor 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture AD06 AE03 AE04 AE05 4J002 BB041 BB201 EX016 EX026 EX036 EX046 EX076 EX086 FD206 GC00 GH00 GJ00 GM00 GQ00 4J038 CA091 CB041 CB091 CB111 CB141 DA151 GA01 GA02 GA09 GA12 GA13 GA03 PC03 DA03 PC03 DA03 PC03 DA03 GA04 GA22 GA23 GA24 GA31 HD33 HD36 JA09 KA16 MA02 MA05 MA06 MA10 NA19 NA20 PA23 4J100 AA01Q AA02P AA03Q AA04Q AA15Q AA16Q AA17Q AA19Q AA21Q AS15R BA71H BA72H CA03 CA04 HA55 HC79 JA01 JA32 JA57 JA57

Claims (19)

[Claims] (1) a non-conjugated 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]; Silyl group-containing ethylene containing a hydrolyzable silyl group represented by the formula [III]:
α-olefin / non-conjugated polyene random copolymer rubber (A), 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, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. And a curable composition comprising an amino-substituted silane compound (X). (A) a silyl group-containing ethylene / α-olefin / non-conjugated polyene random copolymer rubber containing a hydrolyzable silyl group (A), and (b) one silanol group in the molecule. A compound (B) capable of producing a compound having one silanol group in the molecule by reacting a compound having the compound and / or a hydrolyzable silicon group in the molecule with water, and the amino group-substituted silane compound ( X)
(C) a compound (C) having a silicon-containing group having two hydrolyzable groups bonded thereto and an amino group, and (d) a silicon having three hydrolyzable groups bonded thereto. The curable composition according to claim 1, further comprising a compound (D) having a group and an amino group. (A) an organic polymer containing a hydrolyzable silyl group represented by the following general formula [III] and having substantially no unsaturated double bond in the main chain: [Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. ] And an amino group-substituted silane compound (X), wherein the curable composition is used for electric / electronic parts, transportation equipment, civil engineering / architecture, medical treatment or recreational use. Characteristic curable composition. (A) an organic polymer containing a hydrolyzable silyl group represented by the above general formula [III] and having substantially no unsaturated double bond in the main chain; and (b) an intramolecular compound. A compound having one silanol group, and / or a compound (B) capable of producing a compound having one silanol group in the molecule by reacting a hydrolyzable silicon group in the molecule with water. (C) Compound (C) having a silicon-containing group to which two hydrolyzable groups are bonded and an amino group as amino-substituted silane compound (X), and (d)
The curable composition according to claim 3, comprising a compound (D) having a silicon-containing group to which three hydrolyzable groups are bonded and an amino group. 5. The use of said electric / electronic parts is heavy electric parts,
Light electrical parts, sealing materials, potting materials, coating materials or adhesives for circuits and substrates of electric and electronic equipment;
4. 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 an encapsulating material for gel or a capacitor.
Or the curable composition according to 4. 6. The curable composition according to claim 5, 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. 7. The high-voltage transformer with a variable resistance section, wherein the potting material is a transformer high-voltage circuit, a printed circuit board,
The curable composition according to claim 5, 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. 8. 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 curable composition according to claim 5, which is used for coating a buffer material for a wire; a semiconductive element; or an optical fiber for optical communication. 9. The curable composition according to claim 5, wherein the adhesive is used for bonding cathode ray tube wedges, necks, electrically insulating parts, semiconductive parts or conductive parts. 10. The curable composition according to claim 3, wherein the use of the transport machine is a use of an automobile, a ship, an aircraft, or a railway vehicle. 11. The use of the automobile is as follows: 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; The curable composition according to claim 10, wherein the curable composition 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. 12. The curable composition according to claim 10, wherein the use of the marine vessel is a wiring junction box, a sealing material for electric system parts or electric wires, or an adhesive for electric wires or glass. object. 13. The civil and architectural uses include 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, a prefabricated joint. 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 curable composition according to claim 3, wherein the curable composition is used for a paint, an adhesive for stone, slate, concrete, or tile; or an adhesive sheet, a waterproof sheet, or an anti-vibration sheet. 14. The curable composition according to claim 3, wherein the medical use is a sealing material for a medical rubber stopper, a syringe gasket, or a rubber stopper for a reduced-pressure blood vessel. 15. The leisure use as a swimming member for a swimming cap, diving mask or earplugs; or a gel cushioning member for sports shoes or baseball gloves.
3. The curable composition according to item 1. (A) an organic polymer containing a hydrolyzable silyl group represented by the following general formula [III] and having substantially no unsaturated double bond in the main chain: [Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. And a curable composition containing an amino-substituted silane compound (X). (A) an organic polymer containing a hydrolyzable silyl group represented by the following general formula [III] and containing substantially no unsaturated double bond in the main chain: [Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. And a curable composition containing an amino group-substituted silane compound (X). (A) an organic polymer containing a hydrolyzable silyl group represented by the following general formula [III] and having substantially no unsaturated double bond in the main chain: [Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. And a curable composition containing an amino group-substituted silane compound (X). (A) an organic polymer containing a hydrolyzable silyl group represented by the following general formula [III] and having substantially no unsaturated double bond in the main chain: [Wherein, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, X is a hydride group, a halogen group, a mercapto group, an alkenyloxy group, an alkoxyl group, an acyloxy group,
A hydrolyzable group selected from a ketoximate group, an amide group, an acid amide group, an aminooxy group, a thioalkoxy group and an amino group, and a is an integer of 0, 1 or 2. And a curable composition containing an amino group-substituted silane compound (X).