JP3150383B2 - 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 using 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 present inventors have made intensive studies in order to solve this problem. As a result, a compound having a carboxyl group is represented by the following general formula (I) HO-R- (CH ₂ ) _{n -CH = CH 2 (I)} ( wherein, R represents a CH ₂ or CH ₂ CH ₂ O, n is 1-7.)

By reacting with a compound having a hydroxyl group and an alkenyl group represented by the formula (1), a compound having a high alkenyl group content can be obtained. In the curing of the compound thus obtained, foaming occurs. The present inventors have found that an evenly cured product can be obtained and arrived at the present invention. That is, the present invention

(A) a compound having a carboxyl group;
Obtained by reacting with a compound having a hydroxyl group and an alkenyl group represented by the general formula (I),
A compound having 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 carboxyl 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 carboxyl group may be on the main chain, terminal or side chain. When this compound having a carboxyl group is specifically expressed, it can be represented by the following formula (II). R ¹ — (COOH) _a (II) 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) -, - C (} CH 3) 2 -, - CH ( phenyl)
_{-, - C (CH 3)} ( phenyl) -, - C (phenyl)
_{2 -, - CH (CH 3} ) CH 2 -, - CH 2 -C (CH
_{3) 2 CH 2 -, -} CH 2 CH (CH 2 CH 3) -, C
_{H 3 CH 2 C (CH 2} -) 2 -, - CH (CH
₂ −) ₂ , (CH ₃ ) ₂ CHCH ₂ —, CH ₃ CH ₂ CH (C
_{H 3) -, (CH 3} ) 2 CHCH 2 CH 2 -, CH 3 C
_{H 2 CH (CH 2 CH 3} ) -, (CH 3) 2 CHCH
_{(CH 3) -, (CH} 3) 2 CHC (CH 3) 2 -, -
_{CH 2 CH (CH 3) CH} 2 CH 2 -, - CH 2 CH
_{(CH 3) CH (CH 3} ) CH 2 -, - CH 2 CHCl
CH ₂ CH ₂ -,

[0007]

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[0008]

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[0009]

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[0010]

Embedded image _{CH 3 CH 2 = CHCH (NH} 2) -, - CH 2 CHC
_{l-, CH 3 CHBr-, CH 3} CHCl-,

[0011]

Embedded image

[0012]

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, the polymer used as R ^1, polyether polymer, for example, polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene - polyoxypropylene copolymers 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 methacrylic acid, acrylates such as ethyl acrylate and butyl acrylate, and vinyl acetate and acrylonitrile , Methyl methacrylate, methacrylic acid, hydroxyethyl methacrylate, acrylic ester copolymers and styrene, wherein the graft polymer obtained by polymerizing a vinyl monomer in an 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.

The compound having a hydroxyl group and an alkenyl group represented by the general formula (I) used in the production of the component (A) in the present invention includes, for example, 9-decen-1-ol, 3-buten-1 -All and ethylene glycol monoallyl ether.

As for the reaction between the compound having a carboxyl group and the compound having a hydroxyl group and an alkenyl group for producing the component (A) in the present invention, various proposals can be made. For example, a method of performing dehydration condensation using sulfuric acid, p-toluenesulfonic acid or the like as a catalyst, a method of reacting a base such as sodium hydride with a compound having a hydroxyl group and an alkenyl group, and esterifying under a basic condition can be used. .

Further, among the above-mentioned compounds having a carboxyl group, those having a copolymerizable double bond are used,
Using a compound obtained by reacting this with a compound having a hydroxyl group and an alkenyl group as a monomer, copolymerizing it with a monomer capable of being homopolymerized or copolymerized with it,
A compound having an alkenyl group can also be synthesized.
Specifically, a method using allyloxyethyl methacrylate or the like obtained by reacting methacrylic acid and ethylene glycol monoallyl ether as a monomer is exemplified.

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) silicon atom one having hydrosilyl groups such _{as, -Si (CH 3) 2 Si} (C
_{H 3) 2 H, -Si (} CH 3) 2 CH 2 CH 2 Si (C
_{H 3) 2 H, -Si (} CH 3) 2 SiCH 3 H 2, -S
i (CH _{3) 2} - _{(phenyl) -Si (CH 3) 2 H} ,
_{-Si (CH 3) 2 NHSi (} CH 3) 2 H, -Si
(CH ₃ ) ₂ N [Si (CH ₃ ) ₂ H] ₂ , —Si (C
_{H 3) 2 OC (CH 3} ) = NSi (CH 3) 2 H, -S
_{i (CH 3) 2 N =} C (CH 3) OSi (CH 3) 2 H
Having two silicon atoms, such as-(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. ]

[0020]

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.

Of 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-Si (CH 3) 3] 2 H

[0023]

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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 (III) can be given. _{(X-CH 2 CH (R} 2 ) -R ³ -O) _a -R ⁴ (III)

The formula, X is a group having a hydrosilyl group as described above one or more, 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 this formula (III), 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_TwoCH_TwoOCH_TwoCH_Two-, -CH
_TwoCH_TwoOCH_TwoCH_TwoCH_Two-And the like. Synthesis
From the above easiness, -CH_Two-Is preferred.
R in this formula (III)^Four Is aliphatic or aromatic
The following are specific examples:
You. CH_Three-, CH_ThreeCH_Two-, CH_ThreeCH_TwoCH_Two−, −
CH_TwoCH (CH_Three)-, -C (CH_Three)_TwoCH_Two−,
-CH (CH_TwoCH_Three) -CH_Two−, (CH_Three)_ThreeC
-, -CH_Two-, -CH (CH_Three)-, -C (CH_Three)
_Two-, -CH (phenyl)-, -C (phenyl) (CH
_Three)-, -C (phenyl)_Two-, -CH_TwoCH_Two−, −
CH (CH_Three) CH_Two-, -CH_TwoCH_TwoCH_Two−, −
CH_TwoCH_TwoCH_TwoCH_Two-, -CH_Two-C (CH_Three)
_TwoCH_Two-, -CH_TwoCH (CH_TwoCH_Three)-, CH_Three
CH_TwoC (CH_Two−)_Two-, CH (CH_Two−)_Two−,

[0027]

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[0028]

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[0029]

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 (III) 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 polymer obtained by hydrogenating a copolymer of polyisoprene, polybutadiene, isoprene or butadiene with acrylonitrile, styrene, etc., and polyacrylic acid ester obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate Ethyl acrylate, acrylate such as butyl acrylate, and vinyl acetate, acrylonitrile, methyl methacrylate, acrylate copolymer with styrene and the like, a graft polymer obtained by polymerizing a vinyl monomer in the organic polymer, Polysulfide-based polymers, nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 66 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 610 by condensation polymerization of hexamethylenediamine and sebacic acid,
Nylon 11 by condensation polymerization of ε-aminoundecanoic acid,
Nylon 1 by ring-opening polymerization of ε-aminolaurolactam
2. Polyamide-based polymers such as copolymerized nylon having two or more components among the above-mentioned nylons, for example, polycarbonate-based polymers produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl phthalate-based polymers, etc. Is mentioned. Further, as the hydrosilyl group-containing compound of the component (B) used in the present invention, a compound having an ester bond represented by the following formula (IV) can also be used. [X-CH ₂ CH (R ² ) -R ³ -OC (O)] _a -R ⁵ (IV)

In the formula, X represents one of the above-mentioned hydrosilyl groups.
A group having at least^Two And R^Three Is the formula (III)
R^Two And R^Three Can be the same as
R^Five Is an aromatic or aliphatic 1 to 4 valent organic group;
Is a positive integer. This R^Five Specifically, the group represented by
Indicate, CH_Three-, CH_ThreeCH_Two-, CH_ThreeCH_TwoCH_Two−, −
CH_TwoCH_Two-,-(CH_Two)_Three-,-(CH_Two)
_Four-,-(CH_Two)_Five-,-(CH_Two)₆-,-(CH
_Two)₇-,-(CH_Two)₈−,

[0032]

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[0033]

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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, having the formula (II)
All the organic polymers exemplified in I) can be suitably used. Further, as the hydrosilyl group-containing compound of the component (B) used in the present invention, a hydrocarbon compound represented by the following formula (V) can also be used. [X-CH ₂ CH (R ² )] _A -R ⁶ (V)

The formula, X is a group having a hydrosilyl group as described above one or more, R ² is, R in formula (III) ² Wherein 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 —,

[0036]

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[0037]

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

[0038]

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 (III) can be suitably used. Furthermore, (B) used in the present invention
As the hydrosilyl group-containing compound of the component, the following formula (V
The compound having a carbonate bond represented by I) can also be used. _{(X-CH 2 CH (R} 2 ) -R ³ —OC (O) O) _a —R ⁷ (VI)

In the formula, X is a group having at least one hydrosilyl group described above, and R ² and R ³ are R
^The same R ² and R ³ can be used, and R ⁷
Is an aliphatic or aromatic organic group, and a is a positive integer. As R ⁷ , 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 —,

[0040]

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[0041]

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[0042]

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 and has the formula (I)
All the organic polymers exemplified in II) 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-described selective hydrosilylation, the stability is generally good because the component (B) contains a hydrosilylation catalyst 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.

The hydrosilylation catalyst which is the component (C) of the present invention includes platinum alone, alumina, silica, carbon black or the like on which solid platinum is supported, 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.

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.

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, 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 or the like 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.

[0052]

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

137.74 g of methacrylic acid, 80.70 g of ethylene glyceryl monoallyl ether, 1.60 g of paratoluenesulfonic acid, 3.2 g of hydroquinone, and 620 mL of toluene are charged into a flask, and the generated water is refluxed under reflux. The reaction was carried out for 22 hours while removing. The reaction mixture was filtered through celite, washed with saturated aqueous sodium bicarbonate, the aqueous layer was extracted with toluene, evaporated, and distilled. After distillation, 82.43 g of a pale yellow liquid was obtained (bp 6).
3 to 64 ° C / 3.0 mmHg). This liquid was allyloxyethyl methacrylate from the NMR spectrum.

3.20 g of styrene, 5.65 g of n-butyl acrylate, 8.51 g of methyl methacrylate, 7.60 g of allyloxyethyl methacrylate, 2.06 g of n-dodecyl mercaptan, 2.54 g of 2,4-dimethylvaleronitrile, toluene A 5 mL toluene solution of an acrylic acid monomer was dropped into a flask in which 10 mL of toluene was kept at 70 ° C. over 5 hours with a syringe pump under a nitrogen atmosphere. After the completion of the dropwise addition, the reaction was further performed for 15 minutes.
The reaction solution was poured into hexane, and the precipitated oligomer was dried under reduced pressure at 80 ° C. for 1 hour to obtain about 18 g of a colorless viscous liquid oligomer. By internal standard method ¹ H
From -NMR, it was found that this oligomer contained 1.88 mmol of alkenyl groups per gram, the number average molecular weight by GPC was 2,400, and an average of 4.5 alkenyl groups per molecule was introduced. Example

In order to examine the curability of the alkenyl group-containing organic polymer produced in the synthesis example, the organic polymer was treated with a hydrosilyl group-containing compound represented by the following formula (VII) and a chloroplatinic acid catalyst solution ( H ₂ PtCl ₆ · 6H ₂ O1.0g
Was dissolved in 1 mL of C ₂ H ₅ OH and 99 mL of dimethoxyethane), and predetermined amounts of toluene were added and mixed well.
The mixture was applied on a PET film, heated at 100 ° C. for a predetermined time, and the gel fraction was calculated from the weight change after immersion in acetone for 24 hours.

[0056]

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

For 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) 1.2 Amount of the hydrosilyl group-containing compound (g) 0.43 Amount of the H ₂ PtCl ₆ catalyst solution (μL) 56.0 Amount of the toluene (g) 0.8 Result Time (minutes) 12 35 10 15 30 60 Gel fraction (%) 88 94 95 96 96 96 97 98 From the above results, it was found that the composition was a high-temperature fast-curing composition. The obtained cured product was uniform without foaming.

[0058]

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.

(56) References JP-A-3-188166 (JP, A) JP-A-3-181565 (JP, A) JP-A-63-35656 (JP, A) (58) Fields investigated (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) General formula (II): R ¹ — (COOH) _a (II) (wherein R ¹ is an aliphatic or aromatic organic group, and a is a positive integer of 2 or more). A carboxyl group of the compound represented by the general formula (I): HO—R— (CH ₂ ) _n —CH ＝ CH ₂ (I) (wherein R represents CH _{2 or} CH ₂ CH ₂ O; Is 1
7 A) a compound having an alkenyl group obtained by reacting a compound having a hydroxyl group and an alkenyl group represented by (b), (B) a compound having at least two hydrosilyl groups in a molecule, and (C) a hydrosilylation catalyst.