JPH05112719A - Curable composition containing alkenylated compound - Google Patents

Abstract

PURPOSE:To provide a curable compsn. which cures in a short time to give a uniform rubberlike cured article. CONSTITUTION:A curable compsn. is prepd. by compounding a compd. having at least one alkenyl group in the molecule and obtd. by reacting a hydroxylated compd. with a compd. of the general formula: X-CO-(CH2)n-CH2-CH=CH2 (wherein X is hydroxyl or halogen; and n is 1-7), a compd. having at least two hydrosilyl groups in the molecule, and a hydrosilylation catalyst as the essential components.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION 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 one or more alkenyl groups in the molecule, and a hydrogen atom bonded to a silicon atom in the molecule have been used. It is known to crosslink with a curing agent having two or more. As a method of synthesizing a compound having an alkenyl group in the above 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 the curing does not proceed sufficiently. In order to obtain a high functionalization rate, a method of using an acid halide such as allyl chloroformate instead of allyl halide is also known, but in curing the compound having an allyl carbonate type alkenyl group obtained by this method, Had a problem that foaming occurs with desorption of propylene.

[0003]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve this problem and found that a compound having a hydroxyl group is reacted with a compound represented by the following general formula (I). It was found that a compound having a high alkenyl group content was obtained, and in the curing of the compound thus obtained, a uniform cured product was obtained without foaming, and the present invention was reached. . _{X-CO- (CH 2) n} -CH 2 -CH = CH 2 (I) ( wherein, X represents a hydroxyl group or a halogen atom, n represents 1
~ 7. )

That is, the present invention provides a compound having at least one alkenyl group in the molecule, which is obtained by reacting a compound having a hydroxyl group (A) with a compound represented by the above general formula (I), The present invention relates to a curable composition containing B) a compound having at least two hydrosilyl groups in the molecule and (C) 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 from low molecular weight compounds to organic polymers can be used. The hydroxyl group may be in the main chain, terminal or side chain. The compound having this hydroxyl group can be specifically expressed by the following formula (II). R ¹ — (OH) _a (II) In the formula, R ¹ Is an aliphatic or aromatic organic group, and a is a positive integer. This R ¹ Specifically, the following can be mentioned. _{CH 3 -, CH 3 (CH} 2) n - [n = 1~10], -
_{(CH 2) n - [n} = 1~10], (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} CH (CH 3) -, (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]

[Chemical 1]

[0007]

[Chemical 2]

[0008]

[Chemical 3]

[0009]

[Chemical 4]

[0010]

[Chemical 5]

[0011]

[Chemical 6] _{- (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, a polyether polymer such as polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and the like can be preferably used. Examples of other polymers that can be used as a polymer having a main chain skeleton are condensation of a dibasic acid such as adipic acid and glycol,
Or polyester-based polymers obtained by ring-opening polymerization of lactones, ethylene-propylene-based copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc., polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, styrene, etc. Copolymer with, polybutadiene, butadiene and styrene, acrylonitrile and other copolymers, polyisoprene, polybutadiene, isoprene or butadiene and acrylonitrile, a polyolefin-based polymer obtained by hydrogenating a copolymer with styrene, Polyacrylic acid ester obtained by radical polymerization of monomers such as ethyl acrylate, butyl acrylate and hydroxyethyl methacrylate, acrylic acid ester 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 polymers, polysulfide polymers, ε-caprolactam development. Nylon 6 by ring polymerization, Nylon 66 by polycondensation of hexamethylenediamine and adipic acid, Nylon 6 by polycondensation of hexamethylenediamine and sebacic acid
10, polyamide 11 by condensation polymerization of ε-aminoundecanoic acid, nylon 12 by ring-opening polymerization of ε-aminolaurolactam, polyamide-based polymer such as copolymer nylon having two or more components among the above nylons, Examples thereof include a polycarbonate-based polymer and a diallyl phthalate-based polymer produced by condensation polymerization of bisphenol A and carbonyl chloride.

Specific examples of the compound represented by the general formula (I) include 10-undecenoyl chloride, 10-undecenoic acid, 4-pentenoyl chloride and 4-pentenoic acid.

Regarding the reaction of the compound having a hydroxyl group with the compound represented by the general formula (I) for producing the component (A) in the present invention, various proposals can be used. For example, in the formula (I), when X is a hydroxyl group, that is, a carboxylic acid, paratoluenesulfonic acid,
A dehydration condensation reaction under acidic conditions such as sulfuric acid, a method of reacting in the presence of a base when X is a halogen atom such as chlorine, that is, an acid halide 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 preferably used, but those having a molecular weight of 1,000 to 20,000 are particularly preferable. The alkenyl group may be at the molecular end 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 becomes longer at the molecular end. 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, but specific examples of the hydrosilyl group-containing 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
Silicon atom two having groups of _{equal, - (SiR 2 -O) m} - (SiR 2) n -H,

[In the formula, 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 described 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 the same as above, m is a positive integer, and n,
p and q are 0 or a positive integer, and 1 ≦ m + n + p + q ≦
50. ]

[0018]

[Chemical 7] [In the formula, R is the same as above, m is a positive integer, n is 0 or a positive integer, and 2 <m + n <50. ] And other groups derived from various chain-like, branched, or 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 from the viewpoint that the compatibility with organic polymers is less likely to be impaired. The following is preferable in view 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], in [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

[0021]

[Chemical 8]

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 2 in at least one molecule, but is preferably 2 to 15 and particularly preferably 3 to 12. When the compound [(A) component] having an alkenyl group is mixed with the hydrosilylation catalyst of the present invention and cured by a hydrosilylation reaction, the number of the hydrosilyl group is 2
If it is less than the above range, poor curing often occurs. Further, when the number of the hydrosilyl groups is more than 15, the stability of the component (B) is deteriorated, and moreover, a large amount of the hydrosilyl groups remains in the cured product even after curing, causing voids and cracks. The hydrosilyl group-containing compound as the component (B) used in the present invention is not particularly limited, but 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)

In the formula, X is a group having at least one hydrosilyl group described above, R ² Is hydrogen or a methyl group, R ³ Is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds, and 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 -, - C
_{H 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH
_{2 -, - CH 2 CH 2} CH 2 CH 2 -,

-CH₂CH₂OCH₂CH₂-, -CH
₂CH₂OCH₂CH₂CH₂-And the like. Synthesis
From the above ease, -CH₂It is preferably −.
R in this formula (III)^Four Is an aliphatic or aromatic
It is a machine base, and specifically the following can be mentioned.
It CH₃-, CH₃CH₂-, CH₃CH₂CH₂-,-
CH₂CH (CH₃)-, -C (CH₃)₂CH₂-,
-CH (CH₂CH₃) -CH₂-, (CH₃)₃C
-, -CH₂-, -CH (CH₃)-, -C (CH₃)
₂-, -CH (phenyl)-, -C (phenyl) (CH
₃)-, -C (phenyl)₂-, -CH₂CH₂-,-
CH (CH₃) CH₂-, -CH₂CH₂CH₂-,-
CH₂CH₂CH₂CH₂-, -CH₂-C (CH₃)
₂CH₂-, -CH₂CH (CH₂CH₃)-, CH₃
CH₂C (CH₂−)₂-, CH (CH₂−)₂-,

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11] 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) -,
Is. Further, R ⁴ in the formula (III) is May be an organic polymer, and various polymers can be used.

Specifically, first, a polyether polymer such as polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-
Polyoxypropylene copolymer and the like can be preferably used.
Examples of other polymers having a main chain skeleton include polyester-based polymers obtained by condensation of dibasic acids such as adipic acid and glycol, or ring-opening polymerization of lactones, and ethylene-propylene-based copolymers. Polymers, polyisobutylene, copolymers of isobutylene and isoprene and the like, polychloroprene, polyisoprene, isoprene and butadiene, acrylonitrile, copolymers of styrene and the like, polybutadiene, butadiene and styrene, copolymers of acrylonitrile and the like, Polyisoprene, polybutadiene, isoprene or a polyolefin polymer obtained by hydrogenating a copolymer of butadiene and acrylonitrile, styrene, etc., and polyacrylic acid ester obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate. Acrylic esters such as ethyl acrylate and butyl acrylate, vinyl acetate, acrylonitrile, methyl methacrylate, acrylate copolymers with styrene and the like, graft polymers obtained by polymerizing vinyl monomers in the organic polymer, Polysulfide polymer, 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 polycondensation 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 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 hydrosilyl group described above.
A group having the above, R² And R³ In the formula (III)
R² And R³ You can use the same as
R^Five Is an aromatic or aliphatic monovalent tetravalent organic group, and a
Is a positive integer. This R^Five A group represented by
Shown, CH₃-, CH₃CH₂-, CH₃CH₂CH₂-,-
CH₂CH₂-,-(CH₂)₃-,-(CH₂)
_Four-,-(CH₂)_Five-,-(CH₂)₆-,-(CH
₂)₇-,-(CH₂)₈-,

[0030]

[Chemical 12]

[0031]

[Chemical 13]

And the like. Of which-
_{CH 2 CH 2 -, - (} CH 2) 3 -, - (CH 2)
_6- , 0-phenyl, m-phenyl and p-phenyl are preferred. Furthermore, R ⁵ May be an organic polymer and has the formula (II
All the organic polymers exemplified in I) can be preferably 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)

In the formula, X is a group having at least one hydrosilyl group described above, R ² Is R ² in formula (III) Can be used 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. 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]

[Chemical 14]

[0035]

[Chemical 15] Etc. Of _{these, - (CH 2) n -} [n = 1~10],

[0036]

[Chemical 16] Is preferred. _{Furthermore, - (CH 2) n -} [n = 1~10]
Is particularly preferable. This R ⁶ May be an organic polymer, and all the organic polymers exemplified in the formula (III) can be preferably used. Further, used in the present invention (B)
As the compound containing a hydrosilyl group, the following formula (V
A 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 represents one of the above hydrosilyl groups.
A group having the above, R² And R³ In the formula (III)
R² And R³ You can use the same as
R⁷ Is an aliphatic or aromatic organic group, and a is a positive integer
Is. This R⁷ As the CH₃-, CH₃CH₂-, CH₃CH₂CH₂-,-
CH₂CH (CH₃)-, -C (CH₃)₂CH₂-,
-CH (CH₂CH₃) CH₂-, (CH₃)₃C-,
-CH₂-, -CH (CH₃)-, -C (CH₃)
₂-, -CH₂C (CH₃)₂CH₂-, -CH₂CH
(CH₂CH₃)-, CH₃CH₂-C (CH₂−)₂
-, CH (CH₂−)₂-,

[0038]

[Chemical 17]

[0039]

[Chemical 18]

[0040]

[Chemical 19] _{- (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 of the organic polymers exemplified in II) can be preferably used.

When an organic polymer is used as the component (B) in the present invention, the polymer may be linear or branched, and any one having a molecular weight of 500 to 50,000 can be preferably used, but Those of ˜20,000 are particularly preferred. The hydrosilyl group as the component (B) may be present at the molecular end or in the molecule, but when a rubber-like cured product is prepared using the composition of the present invention, it is effective at the molecular end. It is preferable because the network chain length becomes long.

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 the molecule is LiAlH ₄ ,
Treatment with a reducing agent such as NaBH ₄ gives Si--C in the compound.
Method for reducing the 1-group to Si-H group, (ii) reacting an organic compound having a functional group X in the molecule with a compound having a functional group Y reacting with the functional group in the molecule and a hydrosilyl group at the same time And (iii) a method in which a polyhydrosilane compound having at least two hydrosilyl groups is selectively hydrosilylated 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. Of these, the method (iii) is particularly preferable.

When the hydrosilyl group-containing compound which is the component (B) is produced by the selective hydrosilylation described above, the hydrosilylation catalyst is contained in the component (B) even after the reaction, so that the stability is generally good. However, if left for a long time or if moisture is mixed in, the Si-H group S
Conversion to i-OH groups occurs, and phenomena such as viscosity increase and gelation are observed. Therefore, it is preferable to include a storage stability improver in the component (B). Examples of such a compound include compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds,
Organic peroxides and the like can be preferably used. The use 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 per 1 mol of the Si—H group-containing compound of the component (B)
It is preferably used in the range of 10 ^-1 mol. This is 10
^This is because if it is ^-6 mol or less, the storage stability of the component (B) will not be sufficiently improved, and if it is 10 ^-1 mol or more, curing will be hindered. The storage stability improvers may be used alone or in combination of two or more.

As the hydrosilylation catalyst which is the component (C) of the present invention, a simple substance of platinum, a simple substance of 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 (eg Pt (C
_{H 2 = CH 2) 2 (} PPh 3) 2 Pt (CH 2 = C
H ₂ ) ₂ Cl ₂ ), platinum-vinylsiloxane complex (for example, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) _m , P
t [(MeViSiO) ₄ ] _m ), platinum-phosphine complex (for example, 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 is a butyl group, Vi is a vinyl group, Ph is a phenyl group, m and n are integers], dicarbonyldichloroplatinum and also described in Ashby US Pat. Nos. 3,159,601 and 3,159,662. Platinum-hydrocarbon composites, as well as Lamoreaux U.S. Pat. No. 3,22.
Platinum alcoholate catalysts as described in 0,972 are also mentioned. In addition, Modic US Patent 3,5
The platinum chloride-olefin composites described in 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,
It is also possible to use two or more types in combination. From the viewpoint of catalytic activity, chloroplatinic acid, a platinum-olefin complex and a platinum-vinylsiloxane complex are preferable.

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

The molar ratio of the hydrosilyl group to the alkenyl group in the components (A) and (B) in the present invention 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 curing and stickiness and low strength can be obtained, and when the molar ratio is more than 5.0, active hydrosilyl groups remain in the cured product even after curing. Since a large amount remains, cracks and voids occur, and a uniform and strong cured product cannot be obtained.

In the present invention, when the components (A), (B) and (C) are mixed and cured, a uniform cured product excellent in deep-curing property can be obtained without causing phenomena such as foaming. can get. The curing conditions are not particularly limited, but generally 0 to 200 ° C., preferably 30 to 150 ° C. for 10 seconds to
It is good to cure for 4 hours. In particular, at a high temperature of 80 to 150 ° C., a material that 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 of the polymer, the molecular weight, etc., but rubber-like to resin-like products can be prepared.

When a cured product is prepared from the composition of the present invention, component (A), which is an essential three component of the composition of the present invention,
In addition to the component (B) and the component (C), a solvent, an adhesion improver, a physical property modifier, a plasticizer, a filler, an antioxidant, an ultraviolet absorber, a metal deactivator, depending on the purpose of use. Antiozonant, light stabilizer, amine radical chain inhibitor,
Various additives such as a phosphorus-based peroxide decomposing agent, a lubricant, a pigment, and a foaming agent can be appropriately added.

[0050]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. Synthesis example

400 g (40 mmol) of terminal hydroxyl group polycaprolactone (number average molecular weight 10,000), 24 g of pyridine, 350 mL of toluene, 100 mL of tetrahydrofuran were added to a round bottom equipped with a stir bar, a thermometer, a dropping funnel, and a nitrogen blowing tube. Place in a flask and add 4 at 60 ° C from the dropping funnel.
0.6 g of undecenoyl chloride was slowly added dropwise. Then, it heated at 85 degreeC and stirred for 13 hours. The formed salt was removed by filtration, washed with 300 mL of a hydrochloric acid aqueous solution, and concentrated to obtain an alkenyl group-terminated polycaprolactone. From the VPO measurement of the obtained oligomer, the number average molecular weight was 10,100. The introduction of the alkenyl group could be confirmed from the spectrum of the olefin portion of NMR. Further, an average of 2.01 alkenyl groups per molecule (0.199
It was confirmed that the amount (mmol / g) was introduced. Example

An alkenyl group-containing organic polymer produced in the synthesis example, a hydrosilyl group-containing compound represented by the following formula (VII), a chloroplatinic acid catalyst solution (H ₂ PtCl ₆ .6H)
A solution of 1.0 g of ₂ O dissolved in ₁ mL of C ₂ H ₅ OH and 99 mL of dimethoxyethane) and benzothiazole (a solution of 1.0 g of benzothiazole dissolved in 9 g of toluene) as a storage stability improver at the ratios shown below. Stir well and mix. The mixture was poured into an aluminum mold, defoamed under reduced pressure at 80 ° C., and then cured at 100 ° C. for 20 hours to obtain a rubber-like cured product having a thickness of about 2 mm and no foaming. It was From the sheet of the cured product, JIS K71
A No. 2 (1/3) dumbbell conforming to No. 13 was punched out and a tensile test was conducted at a pulling speed of 200 mm / min.

[0053]

[Chemical 20] This formulation and its result are shown below. Formulation Amount of polymer used in Synthesis Example (g) 19.7 Amount of compound containing hydrosilyl group (g) 9.9 H ₂ PtCl ₆ Amount of catalyst solution (μL) 6.1 Amount of benzothiazole solution ( μL) 47.9 Results Tensile properties Eb (%) 698 Tb (Kgf / cm ² 379 From the above results, it was found that the composition of the present invention can be cured in a short time to produce a uniform rubber-like cured product.

[0054]

The curable composition of the present invention can be cured in a short time to obtain a uniform rubber-like cured product.

Claims (1)

[Claims] 1. A curable composition comprising the following components (A), (B) and (C) as essential components. A compound having (A) a hydroxyl group, the general formula (I) X-CO- (CH 2) n -CH 2 -CH = CH 2 (I) ( wherein, X represents a hydroxyl group or a halogen atom, n Is 1
~ 7. ) At least one alkenyl group in the molecule, which is obtained by reacting with a compound represented by
A compound having at least two hydrosilyl groups in the molecule, and (C) a hydrosilylation catalyst.