JP3150381B2 - Curable composition containing a compound having an alkenyl group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition containing a compound having an alkenyl group.

[0002]

2. Description of the Related Art Conventionally, as a curable composition which cures to form a rubber-like substance, a compound having at least one alkenyl group in a molecule includes a compound having a hydrogen atom bonded to a silicon atom in the molecule. What crosslinks with a curing agent having two or more is known. As a method for synthesizing a compound having an alkenyl group in the curing system, a method of reacting a compound having a hydroxyl group with allyl halide under basic conditions is known.
However, this method has a problem that a high degree of functionalization cannot be obtained depending on the substrate, and curing does not proceed sufficiently. In order to obtain a high functionalization rate, a method using an acid halide such as allyl chloroformate instead of allyl halide is also known.However, in curing a compound having an alkenyl group of an allyl carbonate type obtained by this method, However, there is a problem that foaming occurs with the desorption of propylene.

[0003]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve this problem, and found that a compound having a hydroxyl group is reacted with a compound having an epoxy group and an alkenyl group. A compound having an alkenyl group content was obtained, and it was found that a uniform cured product without foaming was obtained in the curing of the compound thus obtained, and the present invention was reached. That is,
The present invention

(A) An alkenyl group obtained by reacting a compound having a hydroxyl group with a compound having an epoxy group and an alkenyl group has at least one alkenyl group in the molecule.
(B) a compound having at least two hydrosilyl groups in a molecule; and (C) a curable composition containing a hydrosilylation catalyst as an essential component. The present invention will be described more specifically.

As the compound having a hydroxyl group used in the production of the component (A) in the present invention, a wide range of compounds ranging from low molecular weight compounds to organic polymers can be used. Further, the hydroxyl group may be in any of the main chain, the terminal and the side chain. Specifically, it can be expressed by the following equation (I). R ¹ — (OH) _a (I) wherein R ¹ Is an aliphatic or aromatic organic group, and a is a positive integer. This R ¹ Specific examples include the following. CH _3- , CH ₃ (CH ₂ ) _n- [n = 1 to 10],-
(CH ₂ ) _n- [n = 1 to 10], (CH ₃ ) ₂ CH
_{-, - C (CH 3)} 2 CH 2 -, - CH (CH 2 C
_{H 3) -CH 2 -, (} CH 3) 3 C -, - CH (C
_{H 3) CH 2 -, -} CH 2 -C (CH 3) 2 CH 2 -,
—CH ₂ CH (CH ₂ CH ₃ ) —, CH ₃ CH ₂ C (C
H ₂ —) ₂ —, —CH (CH ₂ —) ₂ , (CH ₃ ) ₂ C
HCH ₂ —, CH ₃ CH ₂ C (CH ₃ ) H—, (C
H ₃ ) ₂ CHCH ₂ CH ₂ —, CH ₃ CH ₂ CH (CH
_{2 CH 3) -, (CH} 3) 2 CHCH (CH 3) -,
_{(CH 3) 2 CHC (CH} 3) 2 -, - CH 2 CH (C
H ₃ ) CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) CH
_{(CH 3) CH 2 -,} - CH 2 CHClCH 2 CH
_2- ,

[0006]

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[0007]

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[0008]

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[0009]

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[0010]

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[0011]

Embedded image _{- (CH 2 CH 2 O)} n CH 2 CH 2 - [n is an integer of from 1 to _{5], - (CH 2 CH (} CH 3) O) n CH 2 CH
(CH ₃₎ - [n is an integer of from 1 to 5], - (CH ₂ CH _{2
CH 2 O) n CH 2 CH} 2 CH 2 - [n is an integer of from 1 to _{5], - (CH 2 CH 2} CH 2 CH 2 O) n CH 2 CH
₂ CH ₂ CH ₂ - [n is an integer of from 1 to 5].

Further, R ¹ May be an organic polymer,
Various polymers can be used. First, R ¹ As the polymer used as the above, a polyether polymer, for example, polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, or the like can be preferably used. Examples of other polymers having a main chain skeleton include condensation of a dibasic acid such as adipic acid with glycol,
Or a polyester polymer obtained by ring-opening polymerization of lactones, an ethylene-propylene copolymer, a copolymer of polyisobutylene, isobutylene and isoprene, polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, styrene, etc. A copolymer with polybutadiene, butadiene and styrene, a copolymer with acrylonitrile, etc., polyisoprene, polybutadiene, isoprene or a polyolefin polymer obtained by hydrogenating a copolymer with butadiene and acrylonitrile, styrene, etc., Polyacrylates obtained by radical polymerization of monomers such as ethyl acrylate, butyl acrylate, and hydroxyethyl methacrylate; acrylates such as ethyl acrylate and butyl acrylate; and vinyl acetate. Acrylonitrile, methyl methacrylate, hydroxyethyl methacrylate, acrylate copolymers with styrene, etc., graft polymers obtained by polymerizing vinyl monomers in the organic polymer, polysulfide polymers, opening of ε-caprolactam Nylon 6 by ring polymerization, Nylon 66 by condensation polymerization of hexamethylenediamine and adipic acid, Nylon 6 by condensation polymerization of hexamethylenediamine and sebacic acid
10, Nylon 11 by condensation polymerization of ε-aminoundecanoic acid, Nylon 12 by ring-opening polymerization of ε-aminolaurolactam, polyamide polymers such as copolymerized nylon having two or more components among the above nylons, For example, a polycarbonate polymer and a diallyl phthalate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride are exemplified.

The compound having an epoxy group and an alkenyl group used in the production of the component (A) in the present invention includes, for example, allyl glycidyl ether, 1-vinyl-
3,4-epoxycyclohexane and the like.

As for the reaction between the compound having a hydroxyl group and the compound having an epoxy group and an alkenyl group for producing the component (A) in the present invention, various proposals can be made. For example, using a protonic acid such as sulfuric acid, a Lewis acid such as tin tetrachloride as a catalyst,
A method of cleaving an epoxy group under acidic conditions, a method of reacting a compound having a hydroxyl group with a base such as sodium hydride, and cleaving the epoxy group under basic conditions can be used.

The alkenyl group-containing compound thus obtained can be suitably used as the component (A) of the curable composition of the present invention. These may be linear or branched, and those having a molecular weight of 100 to 50,000 can be suitably used, and those having a molecular weight of 1,000 to 20,000 are particularly preferable. The alkenyl group may be present at the molecular terminal or in the molecule, but when a rubber-like cured product is prepared using the composition of the present invention, the effective network chain length is longer at the molecular terminal because it is longer at the molecular terminal. preferable.

The compound having at least two hydrosilyl groups in the molecule, which is the component (B) of the present invention, is not particularly limited. Specific examples of the group containing the hydrosilyl group include -Si (H ) _N (CH ₃ ) _3-n , -Si
(H) _n (C ₂ H ₅ ) _3-n , —Si (H) _n (C
_{6 H 5) 3-n [} n = 1~3], - SiH 2 (C 6 H 13)
Such as a hydrosilyl group having one silicon atom, -Si (C
_{H 3) 2 Si (CH 3} ) 2 H, -Si (CH 3) 2 CH
_{2 CH 2 Si (CH 3)} 2 H, -Si (CH 3) 2 Si
_{CH 3 H 2, -Si (CH} 3) 2 ( phenyl) Si (C
_{H 3) 2 H, -Si (} CH 3) 2 NHSi (CH 3) 2
_{H, -Si (CH 3) 2} N [Si (CH 3) 2 H] 2,
_{-Si (CH 3) 2 OC (} CH 3) = NSi (CH 3)
_{2 H, -Si (CH 3)} 2 N = C (CH 3) OSi (C
A hydrosilyl group having two silicon atoms such as H ₃ ) ₂ H,
— (SiR ₂ —O) _m — (SiR ₂ ) _n —H,

[Wherein, R is a group selected from H, OSi (CH ₃ ) ₃ and an organic group having 1 to 10 carbon atoms, and each R may be the same or different. m and n are positive integers and 2 <m + n <50. ] -Si (R) [(O-SiH (R)-) _m- R] [(O
—SiH (R) —) _n —R], wherein R, m and n are the same as above. ] -Si (R) [-(O-SiH (R)-) _m (O-Si
R _2- ) _p -R] [-(O-SiH (R)-) _n (O-
SiR ₂ -) _q -R] [wherein, R is as defined above, m is a positive integer, n,
p and q are 0 or positive integers, and 1 ≦ m + n + p + q ≦
50. ]

[0018]

Embedded image [Wherein, R is the same as above, m is a positive integer, n is 0 or a positive integer, and 2 <m + n <50. And the like, which are derived from various kinds of chain, branched and cyclic polyvalent hydrogen siloxanes.

Among these various hydrosilyl groups, the molecular weight of the group constituting the hydrosilyl group of the hydrosilyl group-containing organic compound of the present invention is 500 or less, since it is unlikely to impair the compatibility with the organic polymer. The following are preferable in consideration of the reactivity of the hydrosilyl group.

-Si (CH ₃ ) [-(O-SiH (CH
_{3) -) p (O-} Si (CH 3) 3] [- (O-SiH
(CH ₃ ) —) _q (O—Si (CH ₃ ) ₃ ], wherein
p is a positive integer, q is 0 or a positive integer, and 2 ≦ p
+ Q ≦ 4. ] -Si [O-Si (CH 3) 3] 2 -O-Si [O-S
_{i (CH 3) 3] 2} H

[0021]

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In the component (B), when two or more hydrosilyl groups are present in the same molecule, they may be the same or different. The total number of hydrosilyl groups contained in the component (B) may be at least two in one molecule, but is preferably from 2 to 15, and particularly preferably from 3 to 12. When mixed with a compound having an alkenyl group [component (A)] and cured by a hydrosilylation reaction in the presence of the hydrosilylation catalyst of the present invention, the number of the hydrosilyl groups is 2
If the amount is smaller, curing failure often occurs. When the number of the hydrosilyl groups is more than 15, the stability of the component (B) deteriorates, and a large amount of the hydrosilyl groups remains in the cured product even after curing, which causes voids and cracks. The hydrosilyl group-containing compound as the component (B) used in the present invention is not particularly limited, and various compounds ranging from low molecular weight compounds to polymers can be used. As a specific example, first, an ether compound represented by the following formula (II) can be given. _{(X-CH 2 CH (R} 2 ) -R ³ -O) _a -R ⁴ (II)

In the formula, X is a group having at least one hydrosilyl group, R ² Is hydrogen or methyl, R ³ It may be contained in one or more ether bonds with a divalent hydrocarbon group having 1 to 20 carbon atoms, R ⁴ Is an aliphatic or aromatic organic group, and a is a positive integer. In the formula (II), R ³ Represents a divalent hydrocarbon group having 1 to 20 carbon atoms, but may contain one or more ether bonds.
_{Specifically, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2
_{-, - CH 2 CH (CH} 3) CH 2 -, - CH 2 CH 2
CH ₂ CH ₂ -,

--CH ₂ CH ₂ OCH ₂ CH _2- , --CH
_{2 CH 2 OCH 2 CH 2 CH} 2 - and the like. From the easiness of synthesis, -CH ₂ - is preferably.
R ⁴ in the formula (II) Is an aliphatic or aromatic organic group, and specific examples include the following. _{CH 3 -, CH 3 CH 2} -, CH 3 CH 2 CH 2 -, -
_{CH 2 CH (CH 3) -} , - C (CH 3) 2 CH 2 -,
—CH ₂ —CH (CH ₂ CH ₃ ) —, (CH ₃ ) ₃ C
_{-, - CH 2 -, -} CH (CH 3) -, - C (CH 3)
_2- , -CH (phenyl)-, -C (phenyl) (CH
₃₎ -, - C _{(phenyl) 2 -, - CH 2 CH} 2 -, -
_{CH (CH 3) CH 2 -} , - CH 2 CH 2 CH 2 -, -
_{CH 2 CH 2 CH 2 CH 2} -, - CH 2 -C (CH 3)
₂ CH ₂ —, —CH ₂ CH (CH ₂ CH ₃ ) —, CH _{3
CH 2 C (CH 2 -)} 2 -, CH (CH 2 -) 2 -,

[0025]

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[0026]

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[0027]

Embedded image Among these, preferred _{are, -CH 2 CH 2 -, -} CH 2 CH (CH 3) -, - ( phenyl) -, - (phenyl) -C (CH _{3) 2} - (phenyl) -, - (phenyl) -CH ₂ - (phenyl) -,
- (phenyl) -SO ₂ - (phenyl) -, - (cyclohexyl) -C (CH _{3) 2} - (cyclohexyl) -,
It is. Further, R ⁴ in the formula (II) May be an organic polymer, and various polymers can be used.

Specifically, first, polyether polymers such as polyoxyethylene, polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-
Polyoxypropylene copolymers and the like can be suitably used.
Examples of other polymers that can be used as a polymer having a main chain skeleton include a polyester-based polymer obtained by condensation of a dibasic acid such as adipic acid with glycol, or a ring-opening polymerization of lactones, and an ethylene-propylene-based copolymer. Polymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, copolymer of styrene and the like, polybutadiene, butadiene and styrene, copolymer of acrylonitrile and the like, Polyolefin polymers obtained by hydrogenating polyisoprene, polybutadiene, isoprene or a copolymer of butadiene with acrylonitrile, styrene, etc., and polyacrylate esters obtained by radical polymerization of monomers such as ethyl acrylate, butyl acrylate, etc. , Ethyl acrylate, and acrylic acid esters such as butyl acrylate, vinyl acetate,
Acrylonitrile, methyl methacrylate, acrylate copolymers with styrene, etc., a graft polymer obtained by polymerizing a vinyl monomer in the organic polymer,
Nylon 6 by ring-opening polymerization of polysulfide polymer, ε-caprolactam, Nylon 66 by condensation polymerization of hexamethylenediamine and adipic acid, Nylon 61 by condensation polymerization of hexamethylenediamine and sebacic acid
Nylon 1 by condensation polymerization of 0, ε-aminoundecanoic acid
1. Nylon 12 by ring-opening polymerization of ε-aminolaurolactam, polyamide polymer such as copolymerized nylon having two or more components among the above-mentioned nylons, for example, produced by condensation polymerization of bisphenol A and carbonyl chloride And a diallyl phthalate polymer. Further, as the hydrosilyl group-containing compound of the component (B) used in the present invention, the following formula (III)
A compound having an ester bond represented by the following formula can also be used. [X-CH ₂ CH (R ² ) -R ³ -OC (O)] _a -R ⁵ (III)

The formula, X is a group having at least one hydrosilyl groups mentioned above, R ² And R ³ Is R in formula (II)
^Two And R ³ Can be the same as
^Five Is an aromatic or aliphatic monovalent to tetravalent organic group, and a is a positive integer. This R ⁵ In the group represented by the specifically _{shown, CH 3 -, CH 3 CH} 2 -, CH 3 CH 2 CH 2 -, -
_{CH 2 CH 2 -, - (} CH 2) 3 -, - (CH 2)
_{4 -, - (CH 2)} 5 -, - (CH 2) 6 -, - (CH
_{2) 7 -, - (CH} 2) 8 -,

[0030]

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[0031]

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And the like. Among them,-
_{CH 2 CH 2 -, - (} CH 2) 3 -, - (CH 2)
_6- , 0-phenyl, m-phenyl and p-phenyl are preferred. In addition, R ⁵ May be an organic polymer, of the formula (I
All the organic polymers exemplified in I) can be suitably used. Further, as the hydrosilyl group-containing compound as the component (B) used in the present invention, a hydrocarbon compound represented by the following formula (IV) can also be used. [X-CH ₂ CH (R ² )] _A -R ⁶ (IV)

The formula, X is a group having a hydrosilyl group as described above one or more, R ² Is R ² in the formula (II) And the same as R ⁶ Is an aliphatic or aromatic organic group, and a is a positive integer. This R ⁶ Represents an aliphatic or aromatic organic group, and specifically, CH ₃ (CH ₂ ) _n- [n = 1 to 10], (CH ₃ ) ₂
CHCH ₂ —, CH ₃ CH ₂ CH (CH ₃ ) —, (CH
₃ ) ₂ CHCH ₂ CH ₂ —, (CH ₃ CH ₂ ) ₂ CH
—, (CH ₃ ) ₂ CHCH (CH ₃ ) —, (CH ₃ ) _{2
CHC (CH 3) 2 -,} - (CH 2) n - [n = 1~1
_{0], - CH 2 CH (} CH 3) CH 2 CH 2 -, - CH
_{2 CH (CH 3) CH (} CH 3) CH 2 -, - CH 2 C
HClCH ₂ CH ₂ —,

[0034]

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[0035]

Embedded image And the like. Among them,-(CH ₂ ) _n- [n = 1 to 10],

[0036]

Embedded image Is preferred. Further,-(CH ₂ ) _n- [n = 1 to 10]
Is particularly preferred. This R ⁶ May be an organic polymer, and all the organic polymers exemplified in the formula (II) can be suitably used. Further, as the hydrosilyl group-containing compound of the component (B) used in the present invention, a compound having a carbonate bond represented by the following formula (V) can also be used. _{(X-CH 2 CH (R} 2 ) -R ³ -OC (O) O) _a -R ⁷ (V)

In the formula, X is a group having at least one hydrosilyl group, R ² And R ³ Is R in formula (II)
^Two And R ³ Can be the same as
⁷ Is an aliphatic or aromatic organic group, and a is a positive integer. This R ⁷ As CH ₃ —, CH ₃ CH ₂ —, CH ₃ CH ₂ CH ₂ —, −
_{CH 2 CH (CH 3) -} , - C (CH 3) 2 CH 2 -,
—CH (CH ₂ CH ₃ ) CH ₂ —, (CH ₃ ) ₃ C—,
_{-CH 2 -, - CH (CH} 3) -, - C (CH 3)
_{2 -, - CH 2 C (} CH 3) 2 CH 2 -, - CH 2 CH
_{(CH 2 CH 3) -,} CH 3 CH 2 -C (CH 2 -) 2
—, CH (CH ₂ —) ₂ —,

[0038]

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[0039]

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[0040]

Embedded image _{- (CH 2 CH 2 O)} n CH 2 CH 2 - [n is an integer of from 1 to _{5], - (CH 2 CH (} CH 3) O) n CH 2 CH
(CH ₃₎ - [n is an integer of from 1 to 5], - (CH ₂ CH _{2
CH 2 O) n CH 2 CH} 2 CH 2 - [n is an integer of from 1 to _{5], - (CH 2 CH 2} CH 2 CH 2 O) n CH 2 CH
₂ CH ₂ CH ₂ - [n is an integer of from 1 to 5], and the like. -CH ₂ Of these CH ₂ OCH ₂ CH ₂ -,
_{-CH 2 CH 2 OCH 2 CH 2} OCH 2 CH 2 -, - C
_{H 2 CH (CH 3) OCH} 2 CH (CH 3) - it is particularly preferred. This R ⁷ May be an organic polymer, of the formula (I
All the organic polymers exemplified in I) can be suitably used.

When an organic polymer is used as the component (B) in the present invention, the polymer may be linear or branched, and any polymer having a molecular weight of 500 to 50,000 can be suitably used. Particularly preferred are those of ~ 20,000. The hydrosilyl group of the component (B) may be at the molecular terminal or in the molecule, but when a rubber-like cured product is prepared using the composition of the present invention, it is more effective at the molecular terminal. This is preferable because the length of the network chain becomes longer.

The method for producing the component (B) of the present invention is not particularly limited, and any method may be used. For example, (i) an organic compound having a Si—Cl group in a molecule is LiAlH ₄ ,
By treatment with a reducing agent such as NaBH ₄ Si-C in the compound
(ii) reacting an organic compound having a functional group X in a molecule with a compound having both a functional group Y and a hydrosilyl group which react with the above functional group in the molecule. (Iii) a method of selectively hydrosilylating a polyhydrosilane compound having at least two hydrosilyl groups with respect to an organic compound having an alkenyl group so that the hydrosilyl group remains in the molecule of the compound even after the reaction. Conceivable. Among these, the method (iii) is particularly preferred.

When the hydrosilyl group-containing compound as the component (B) is produced by the above-mentioned selective hydrosilylation, the stability is generally good because the hydrosilylation catalyst is contained in the component (B) even after the reaction. In addition, when left for a long time or when moisture is mixed in,
Conversion to i-OH groups occurs, and phenomena such as an increase in viscosity and gelation are observed. Therefore, it is preferable to include a storage stability improver in the component (B). Such compounds include compounds containing aliphatic unsaturated bonds, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin-based compounds,
Organic peroxides and the like can be suitably used. The amount of the storage stability improver can be selected almost arbitrarily as long as it is uniformly dispersed in the components (A) and (B).
10 ^{-6 with respect} to 1 mol of the Si-H group-containing compound (B).
It is preferably used in the range of 10 to 10 ^-1 mol. This is 10
^{When the} amount is less than ^-6 mol, the storage stability of the component (B) is not sufficiently improved, and when the amount is more than 10 ^-1 mol, curing is inhibited. The storage stability improvers may be used alone or in combination of two or more.

Examples of the hydrosilylation catalyst which is the component (C) of the present invention include platinum alone, alumina, silica, carbon black or the like with solid platinum supported thereon, chloroplatinic acid, chloroplatinic acid and alcohol, Complexes with aldehydes, ketones, etc., platinum-olefin complexes (for example, Pt (C
_{H 2 = CH 2) 2 (} PPh 3) 2 Pt (CH 2 = C
H ₂ ) ₂ Cl ₂ ), a platinum-vinylsiloxane complex (for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _m , P
t [(MeViSiO) ₄ ] _m ), a platinum-phosphine complex (eg, Pt (PPh ₃ ) ₄ , Pt (PB
u _{3) 4),} platinum - phosphite complex (e.g., Pt
[P (OPh) ₃ ] ₄ ), wherein Me is a methyl group, B
u represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and m and n represent integers], dicarbonyldichloroplatinum, and described in Ashby U.S. Pat. Nos. 3,159,601 and 3,159,662. Platinum-hydrocarbon complexes, and Lamoreaux U.S. Pat.
Also included are the platinum alcoholate catalysts described in U.S. Pat. No. 0,972. Further, Modic U.S. Pat.
The platinum chloride-olefin complexes described in U.S. Pat. No. 16,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ and RhAl ₂
O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl
₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _{4 and the} like. These catalysts may be used alone,
Two or more kinds can be used in combination. From the viewpoint of catalytic activity, chloroplatinic acid, a platinum-olefin complex, and a platinum-vinylsiloxane complex are preferred.

The amount of the catalyst which is the component (C) of the present invention is not particularly limited, but the amount of the alkenyl group 1 in the component (A) is not limited.
It is preferable to use 10 ^-1 to 10 ^-8 mol per mol. Preferably, it is used in the range of 10 ^-3 to 10 ^-6 mol. If the amount is less than 10 ^-8 mol, the curing does not proceed sufficiently. Further, the hydrosilylation catalyst is generally expensive and corrosive, and a large amount of hydrogen gas may be generated to foam a cured product. Therefore, it is better not to use the hydrosilylation catalyst in an amount of 10 ^-1 mol or more.

In the present invention, the molar ratio of the hydrosilyl group to the alkenyl group of the component (A) and the component (B) is preferably 0.2 to 5.0, and more preferably 0.4 to 2.5. . When the molar ratio is less than 0.2, only a cured product with insufficient strength and stickiness is obtained, and when the molar ratio is greater than 5.0, active hydrosilyl groups remain in the cured product even after curing. Since a large amount remains, cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

In the present invention, if the component (A), the component (B) and the component (C) are mixed and cured, a uniform cured product having excellent deep curability without foaming phenomenon can be obtained. can get. The curing conditions are not particularly limited, but are generally 0 to 200 ° C, preferably 30 to 150 ° C for 10 seconds to
It is good to cure for 4 hours. Particularly, at a high temperature of 80 to 150 ° C., a resin which cures in a short time of about 10 seconds to 1 hour can be obtained. The properties of the cured product depend on the molecular structures of the components (A) and (B) used, the main chain skeleton and molecular weight of the polymer, and the like, but can be prepared from rubber to resin.

When a cured product is prepared from the composition of the present invention, component (A), which is the essential three components of the composition of the present invention,
In addition to the components (B) and (C), depending on the purpose of use, solvents, adhesion improvers, physical property modifiers, plasticizers, fillers, antioxidants, ultraviolet absorbers, metal deactivators, Ozone deterioration inhibitor, light stabilizer, amine radical chain inhibitor,
Various additives such as a phosphorus peroxide decomposer, a lubricant, a pigment, and a foaming agent can be appropriately added.

[0050]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these. Synthesis example

10.00 g of methyl methacrylate, 2.60 g of hydroxyethyl methacrylate, 1.00 g of n-dodecylmercaptan, 0.12 g of azobisisobutyronitrile and 50.00 g of isopropyl alcohol were charged into a flask and reacted under reflux for 3 hours. I let it. The isopropyl alcohol was distilled off under reduced pressure to obtain 11.58 g of a white oligomer. To 5 g of the oligomer, 40 mL of toluene, 3.65 g of allyl glycidyl ether,
0.63 g of tin tetrachloride was added, and the mixture was reacted under reflux for 13 hours. The reaction mixture was poured into hexane, and the precipitated oligomer was dried under reduced pressure to give a white oligomer 2.2.
0 g was obtained. By internal standard method ^{From 1} H-NMR, it was found that this oligomer contained 1.00 mmol / g of alkenyl groups per g, had a number average molecular weight by GPC of 1,400, and an average of 1.40 alkenyl groups per molecule was introduced. . Example

In order to examine the curability of the alkenyl group-containing organic polymer produced in the synthesis examples, the organic polymer, a hydrosilyl group-containing compound represented by the following formula (VI), and a chloroplatinic acid catalyst solution (H the ₂ PtCl ₆ · 6H _{2 O1.0g,}
A predetermined amount of a solution dissolved in 1 mL of C ₂ H ₅ OH and 99 mL of dimethoxyethane) and xylene were added and mixed well. The mixture was applied on a PET film, heated at 120 ° C. for 20 minutes, and the gel fraction was calculated from the weight change after immersion in acetone for 24 hours.

[0053]

Embedded image The composition of the composition using this polymer and the results are shown below.

In the compounding, the polymer of the synthesis example and the hydrosilyl group-containing compound were weighed so that the molar ratio between the hydrosilyl group and the alkenyl group was 1 / 1.25. Further, the catalyst solution was added such that Pt was 5 × 10 ⁻⁴ equivalent to the alkenyl group of the polymer of the synthesis example. Formulation Amount of the polymer used in the synthesis example (g) 0.3 Amount of the hydrosilyl group-containing compound (g) 0.06 Amount of the H ₂ PtCl ₆ catalyst solution (μL) 7.77 Amount of xylene (g) 0.6 Results Gel Fraction (%) 83 From the above results, it was found that the composition was high-temperature fast-curing. The obtained cured product was uniform without foaming.

[0055]

As described above, the curable composition of the present invention has high temperature and rapid curability, and a uniform cured product without foaming can be obtained.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-188166 (JP, A) JP-A-3-181565 (JP, A) JP-A-63-35656 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 C08G 77/50-77/52

Claims (1)

(57) [Claims] 1. A curable composition comprising the following components (A), (B) and (C) as essential components. (A) Formula (I): R ^1- (OH) _a (I) (wherein R ¹ is an aliphatic or aromatic organic group, and a is a positive integer of 2 or more). A compound having an alkenyl group obtained by reacting a hydroxyl group of the represented compound with a compound having an epoxy group and an alkenyl group, (B) a compound having at least two hydrosilyl groups in a molecule, and (C) Hydrosilylation catalyst.