JPH0453874A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable composition which is rapidly curable excels in deep curability and is good in mechanical properties by mixing a nonpolymeric organic compound having a plurality of hydrosily groups with an alkenylated organic polymer and a microencapsulated hydrosilyation catalyst. CONSTITUTION:A curable composition is obtained by using a nonpolymeric organic compound having at least two hydrosilyl groups in the molecule [e.g. an organic compound having a group of formula I (wherein R is H, a group of formula II or a 1-10C hydrocarbon group; m is a positive integer; n, p and q are each 0 or a positive integer; and 1<=m+n+p+q<=50) or formula III (wherein R is as defined above; m is a positive integer; n is 0 or a positive integer; and 2<=m+n<=50)], an organic polymer having a molecular weight of 500-50000 and at least one alkenyl group in the molecule [e.g. a polymer having an alkenyl group of formula IV (wherein R<1> is H or CH3)] and a microencapsulated hydrosilylation catalyst (e.g. microencapsulated chloroplatinic acid catalyst) as essential components. This composition excels in storage stability, is rapidly curable and can give a cured product of excellent deep curability and sufficient mechanical properties.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a curable composition, and more specifically, (A)
Contains few (both 2 hydrosilyl groups) in the molecule,
non-polymer organic compound, (B) at least one in the molecule;
Molecular weight containing 500 to 5000 alkenyl groups
The present invention relates to a curable composition comprising an organic polymer of 0 and (C) a microencapsulated hydrosilylation catalyst as an essential component.

[Prior Art and Problems] Various types of curable liquid compositions that are cured to produce rubber-like substances have been developed.

Among these, as a curing system with excellent deep curability, polyorganosiloxane has an average of two or more vinyl groups per molecule at the end or in the molecular chain, and a polyorganosiloxane containing hydrogen atoms bonded to silicon atoms per molecule. A product cross-linked with two or more polyorganohydrodiene siloxanes was developed,
Utilizing its excellent weather resistance, water resistance, and heat resistance, it is used as a sealing agent, potting agent, and knotting agent. However, the use of this system is limited due to its high cost, poor adhesion, and easy mold growth.

Furthermore, the above-mentioned polyorganosiloxanes generally have poor compatibility with organic polymers, and even if attempts are made to cure polyorganosiloxanes and alkenyl-containing organic polymers, phase separation will cause polyorganosiloxanes to form. There was a problem in that the hydrolysis and dehydrogenation condensation reactions of 1 and 2 were promoted, and sufficient mechanical properties could not be obtained due to voids.

[Means for solving the problems] In view of the above-mentioned circumstances, the present invention has been made as a result of intensive research and has solved these problems, and has fast curing properties, excellent deep hardening properties, and sufficient mechanical properties. A curable liquid composition is provided.

That is, if a compound containing at least two hydrosilyl groups in the molecule is used instead of the polyorganohydrothene siloxane conventionally used in the curing reaction by hydrosilylation, it is possible to use a compound containing at least two hydrosilyl groups in the molecule. , has good compatibility with organic polymers containing alkenyl groups.

Furthermore, microencapsulation of the hydrosilylation catalyst exhibits long-term storage stability at ambient temperature;
It is possible to provide one-part or two-part l-curable compositions that cure rapidly at temperatures of 0 to 80°C or higher.

Therefore, by curing both of the above components using a microencapsulated hydrosilylation catalyst, a curable composition that is uniform, has excellent fast curing and deep curing properties, and the cured product has sufficient mechanical properties such as tensile properties. The inventors have discovered that a product can be obtained and have arrived at the present invention.

That is, the present invention comprises the following components (A), (B) and (C).
A curable composition comprising as essential components; (A) a non-polymeric organic compound containing at least two hydrosilyl groups in the molecule; (B) a curable composition containing at least one alkenyl group in the molecule and having a molecular weight of 500 ~50,000 organic polymer, (C) microencapsulated hydrosilylation catalyst.

There is no particular restriction on the non-polymer organic compound containing a small number (both 2 hydrosilyl groups) in the molecule, which is the component (A) of the present invention, but the general formula % formula % () (wherein, X is A substituent containing at least one hydrosilyl group (R2 is a divalent hydrocarbon group having 2 to 20 carbon atoms and may contain one or more ether bonds) in the molecule. There are two compounds.

To describe component (B) more specifically, the square formula (II
I) (X-R"-0→T-R' (I[I)(
In the formula, X, R'' are the same as above, and R3 has 1 to 3 carbon atoms.

(a is an integer selected from 1 to 4).

In 2 (I[I), R2 represents a divalent hydrocarbon group having 2 to 2 o carbon atoms, but R2 may contain one or more ether bonds. Specifically, one CH2C
H2, -CH2CH2CHzH3 CH3CH2H2, CHzCHz(JIzCH
zCH, CH20-CHzC)12-, -(J12C
Examples include H2Cl-CH2CH2CH2. From the viewpoint of ease of synthesis -F, 1 CHzCIIzCHz- is preferred.

In formula (I[[), R3 is an aromatic or aliphatic monovalent to tetravalent organic group having 1 to 30 carbon atoms. Specifically, CL-, CH3CH2-, CI(, CH2C)
l.

CH.

CH3 CH.

CH.

CH3 CIIzCHz CH3 C) 12CH, CH2 CI(2C)I, CH2C)12 H2CH Cl+□ CH3 CH.

CH3 CH2 Hz (CLFi- (n is an integer from 2 to 10) Examples include. Behind these, is preferred.

CHz The following (wherein, X is a group containing at least one hydrosilyl group, R2 is a divalent hydrocarbon group having 2 to 20 carbon atoms, and may contain one or more ether bonds.

R4 is an organic group having 1 to 30 carbon atoms, and a is an integer selected from 1 to 4. ) Compounds having a polyester bond shown in the following are mentioned.

In formula (IV), R2 is the same as R2 in formula (III), and R' is an aromatic or aliphatic group having 1 to 30 carbon atoms.
- It is a tetravalent organic group. To be specific, CH3,
CLCHz, CH3CHzCH2(CHz)s
, (CHz) b-1 (CHz) ? Hx Next, (X-1i” -gFormula (IV) C→i-1?' I (IV) H3 CHi(CH2)? HOC82CH2 CH3 CHzCHzCHCH CH2 cH,CHz=CHCH- I H2CH CIGHzC)IzCH CH3 CH3 CH2 = C (CH2)2 C112=CH CH, CB=CHCH2 (C)+2)3 C11, CH CH CH, =CH-CH2 (CH2).

3C CH3 CH, -C CHi CL(C)Iz)s cn:+(cox)x CH3CHICH CH CHi (CHz)4 CH:+(CHz)a- CH.

CHi C)1. -CH C1, CCH! Examples include.

Among these, the following is preferable.

(CHz)2 ~. - (CH2)3,
(CH2)6CH.

(CH,)2CHCH CH3 (CHff)ZC)Ic CH3 (CHz) ,1 (n□2-10)CH3 C)IzCHC)IzCHz H3cHs CHzCHHCII□ Next, general formula (V) X, -R' (V) (wherein, Examples include compounds having hydrogen as the main chain skeleton.

In formula (V), R5 represents a mono- to tetravalent hydrocarbon group having 2 to 50 carbon atoms, specifically CHa (CHz), -(n=1-10), C
H3(CHx) zcHcHz-1CHiCHzCHH
2CH3 CH,CH,C)l-, (CH,)ffiCHCllf
CH, - Of these, (CHz) (Rho 2-10).

is preferred.

Furthermore, -(CL), (n-2=10) is particularly preferred.

Specific examples of component (A) include the general formula % ()] (wherein, X is a group containing at least one hydrosilyl group, and R2 is a divalent hydrocarbon group having 2 to 20 carbon atoms. It may contain one or more ether bonds.

Rh is a monovalent to tetravalent organic group, and a is an integer selected from 1 to 4. ) Compounds having a carboxylic bond represented by the following formulas are mentioned.

In the formula, R2 is the same as R2 in formulas (I[I) and (IV).

Also, RL is C) I:l-1CHxCHz
, cLc)12cLH,C CHl CH3 CH.

Hi CH2CH3 CH, C)l - CH3 HiCHHz Hz CH CH.

(CHz-Soup1□ (n is an integer from 2 to 10) -(CH20H□0)llCH, CII- (n is 1...
Integer of 5) CH, CH3 Gate C) 12cHO1). C) IzCH (n is an integer from 1 to 5) - (CHzCHzCl(zo)nCHzCHzCH
z-(n is an integer of I-5) HCHzCtlzCHzC)
IzO)-CHzCHzCHzCHz (n is 1 to 5
), etc. Among these, the following are particularly preferred.

CHzCHzOCHzCIlz C)1. CH20CH, CH20C11, CII.

CHzCHOCHzCH CHCH3CH3 In the formulas (I[l), (IV), (V), (V[), X represents a group containing at least one hydrosilyl group, and specific examples include 5i(H) -(CHx)z-
3i(H)fi(CJs)z-,,,Si([1),,
(CJ5)+-,, (n=1~3), 5iH
Hydrosilyl group containing only silicon atoms such as z(Ca)11x), 5i(C1h)zSi(CHx)
ZH,Si (C1l+) zcHzcfl,si (
CH:l) zH5i(CL)zSi(CH:+)Hz
,7F-\s r (CHz) z--9ba5i (Ctlx) z
H3i (CHI)zNl(Si(CI(*)zH,S
i (CL)zN [Si (CH3)zHsi.

Hydrosilyl group containing two or more silicon atoms, such as CH3Si(CH3)zOc=Nsi(CHa)zHH3S+(CHx)zN=CO5+(C)li)zH, R -←5l-Oi→-5i7'' RR ( In the formula, R is a group selected from hydrogen, an alkyl group having 10 or less carbon atoms, an aryl group, and O(CH:+)y, and each R may be the same or different. mn is a positive integer. and 2≦m+n≦20) (wherein R is the same as above, p is a positive integer, q is 0 or a positive integer, and 2≦p+q≦4) Frosilyl group, etc. can be mentioned.

Among the above-mentioned various hydrosilyl groups, the molecular weight of the substituted 5 is preferably 500 or less, and further considering the reactivity of the hydrosilyl group, the following are preferred for C7.

(In the formula, R is the same as below. m is a positive integer, n, pq
is O or a positive integer, and 1≦mtenn+p+q≦
50) (wherein R is the same as above, 0m is a positive integer, n is O or a positive integer, and 2≦m+n≦50). hilh derived from dienesiloxane (wherein R is the same as above, p is a positive integer, q is O or a positive integer, and 2≦p+q≦4)O5i (CH3
) z 05i(CH*) 3-5i-0-Si −
H 05i(CHs)s 0Si(CI(:+lhCH,
H \7/ CH8 CH.

L CH3 C1l.

CH3 CH3 CH.

C8° When two or more substituents X exist in the same molecule, they may be the same or different.

The total number of hydrosilyl groups contained in formulas (III) to (Vl) should be at least 2 in one molecule, preferably 2 to 15, and particularly preferably 3 to 12. When the hydrosilyl group-containing organic compound of the present invention is mixed with various organic polymers containing alkenyl groups in the presence of a hydrolylation catalyst and cured by a hydrosilylation reaction, the number of hydrosilyl groups is less than 2. Curing is slow (often causing poor curing. Also, if the number of hydronolyl groups exceeds 15, the stability of the compound deteriorates, and furthermore, a large amount of hydrosilyl groups remains in the cured product even after curing. This may cause voids or cranks.

There are no particular limitations on the method for producing the hydrosilyl group-containing organic compound of the present invention, and any method may be used.

For example, (11) a method in which an organic compound having a Si -CH group in the molecule is treated with a reducing agent such as LiAIHn + NaBH4 to reduce the 5i-CH group in the compound to a 5i-H group; A method of reacting an organic compound having a certain functional group Among these methods, method (iii) is particularly preferred by selectively hydrosilylating a polyhydrosilane compound having a hydrosilyl group such that the hydrosilyl group remains in the molecule of the compound even after the reaction.

The component (B) used in the present invention contains at least one alkenyl group in the molecule and has a molecular weight of 500 to 5.
As the organic polymer of 0000, those having various main chain skeletons can be used.

First, as the polyether polymer, for example, polyoxyethylene, polyoxypropylene, polyoxytetramethylene, polyoxyethylene polyoxypropylene copolymer, etc. are preferably used. Other polymers with main chain skeletons include polyester polymers obtained by condensation of dibasic acids such as adipic acid with glycol or ring-opening polymerization of lactones, ethylene-propylene copolymers, polyisobutylene, Copolymers of isobutylene and isoprene, etc., polychloroprene, polyisoprene, copolymers of isoprene and butadiene, acrylonitrile, styrene, etc., polybutadiene, copolymers of butadiene and styrene, acrylonitrile, etc., polyisoprene, polybutadiene, isoprene Alternatively, polyolefin polymers obtained by hydrogenating copolymers of butadiene and acrylonitrile, styrene, etc., polyacrylic esters, ethyl acrylate, butyl acrylate, etc. obtained by radical polymerization of monomers such as ethyl acrylate, butyl acrylate, etc. acrylic ester copolymers of acrylic esters and vinyl acetate, acrylonitrile, methyl methacrylate, styrene, etc., graft polymers obtained by polymerizing vinyl monomers in the above organic polymers, polysulfide polymers, ε- Nylon 6 produced by ring-opening polymerization of aminocaprolactam, nylon 66 produced by condensation polymerization of hexamethylene diamine and adipic acid, nylon 610 produced by condensation polymerization of hexamethylene diamine and sebacic acid,
Nylon 11 produced by polycondensation of ε-aminoundecanoic acid,
Nylon 1 produced by ring-opening polymerization of ε-aminolaurolactam
2. Polyamide-based polymers such as copolymerized nylons containing two or more of the above nylon components, such as polyamide-based polymers produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl phthalate-based polymers, etc. Examples include merging.

Among the above-mentioned polymers having a chain skeleton, polyether polymers, acrylic ester polymers, and acrylic ester copolymers are preferred because they have good compatibility with the hydrosilyl group-containing organic compound of component (A). Polymers, hydrocarbon polymers, and polyester polymers are preferred.

Various methods have been proposed for introducing alkenyl groups into the polymer, but they can be roughly divided into methods of introducing alkenyl groups during polymerization and methods of introducing alkenyl groups after polymerization. can.

As a method for introducing an alkenyl group during polymerization, for example, when producing the organic polymer of the present invention by a radical polymerization method, a vinyl monomer containing an alkenyl group with low radical reactivity in the molecule such as allyl methacrylate or allyl acrylate can be used. By using a radical chain transfer agent having an alkenyl group with low radical reactivity such as allyl mercaptan, an alkenyl group can be introduced into the main chain or terminal of the polymer.

As a method for introducing an alkenyl group after polymerization, for example, an active group and an alkenyl group that are reactive toward the above-mentioned functional groups are added to an organic polymer having a functional group such as a hydroxyl group or an alkoxide group at the terminal, main chain, or side chain. An alkenyl group can be introduced into the terminal, main chain, or side chain by reacting an organic compound having the following. Examples of organic compounds having active groups and alkenyl groups that are reactive with the above-mentioned functional groups include acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride, acrylic acid bromide, etc.
, -C2° unsaturated fatty acids, acid halides, acid anhydrides, etc. and allyl chloroformate (CIlt=C[cHzOcO
cI), allyl chloroformate (CL = CHCH
C3Cz such as zOCOBr). unsaturated fatty acid substituted carbonic acid halide, allyl chloride, allyl bromide, vinyl(chloromethyl)benzene, allyl(chloromethyl)
Benzene, allyl (bromomethyl)benzene, allyl (
chloromethyl)ether, allyl(chloromethoxy)benzene, 1-butenyl(chloromethyl)ether, I-
Examples include hexenyl (chloromethoxy)benzene and allyloxy (chloromethyl)benzene.

As the microencapsulated hydrosilylation catalyst which is component (C) in the present invention, microencapsulated various known hydrosilylation catalysts are used.

Specific examples of hydrosilylation catalysts include simple platinum, solid platinum supported on a carrier such as alumina, phosphoric acid, carbon brane, and phosphorus, chloroplatinic acid, and complexes of chloroplatinic acid and alcohols, aldehydes, ketones, etc. , platinum-olefin complex (e.g. pt<cH2・CHz)z(PPhi)
zPt((Jlz・CHz)zclzl: platinum-vinylloxane complex (e.g., PL, , (ViMe2S
iO5iMezv+)*, Pt[(MeViSi
O)al ml; platinum-phosphine complex (e.g., Pt(PPh:+)4, PL(PBLIi)a
l ; platinum-phosphite complex (e.g., Pt (P
(OPh:+] a, PL (P(OBu):+ )
a l (wherein, Me is a methyl group, Bu is a butyl group,
(Vi represents a vinyl group, ph represents a phenyl group, and n and m represent integers), dicarbonyldichloroplatinum, and U.S. Pat. No. 3,159,601 and 3 of Ashby
Also mentioned are the platinum-hydrocarbon complexes described in US Pat. Furthermore, Modic
Also useful in the present invention are platinum chloride olefin complexes described in U.S. Pat.

In addition, examples of catalysts other than platinum compounds include RhC1 (
PPh3)3. RhCl, Rh1AIzOi,
RuCl3. IrCl,, FeCl3. AIC
II, PdCl2・211zO, N+CI□, Ti
Examples include Cl4. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, opposed-olefin complexes, platinum-vinylsiloxane complexes, and the like are preferred.

Polymers useful as microcapsules in which the hydrosilylation catalyst is encapsulated are preferably thermoplastic organic polymers that are insoluble in the catalyst and impermeable to the catalyst. Examples of the former include ethylene, styrene, vinyl chloride, vinylidene chloride, Polymers or copolymers such as acrylonitrile, esters of acrylic acid or tactacrylic acid may be used, examples of the latter include polyamides and polyesters, and also mixed esters such as cellulose acetate esters and cellulose acetate butyralate. Preferably, these thermoplastic organic polymers account for at least 50%, more preferably 70%, of the total weight of the encapsulated catalyst. Below 50%, the catalyst within the capsule may diffuse through the polymer layer forming the capsule.

One preferred method for "microencapsulating" the hydrosilylation catalyst is to precipitate the encapsulating polymer in a solubilized state as part of the separate phase from an emulsion that also contains the catalyst composition. In the first step of the process, the catalyst in the form of fine solid particles or droplets is dispersed in the encapsulant polymer solution.If the catalyst is a liquid, it may optionally be adsorbed onto the surface of solid particles.

The solvent for the encapsulating polymer must be immiscible with the continuous phase of the emulsion, such as water, organic solvents or liquid organosiloxanes. Additionally, the boiling point of the encapsulant solvent or the azeotrope of the solvent and the continuous phase of the emulsion must be lower than the boiling point of the encapsulating polymer.

As a second step, an encapsulant phase is precipitated around the catalyst to be encapsulated. For this precipitation to occur, a force is required to promote adsorption of the encapsulant on the surface of the catalyst to be encapsulated.

In the third step, the mounting medium is solidified. As a coagulation means,
The means used to separate the mounting medium in the second step may be continued, or the mounting medium may be coagulated due to chemical bond formation. The microencapsulated catalyst thus produced is isolated using conventional filtration and drying techniques.

If the catalyst is present on the outer surface of the microcapsules encapsulating the catalyst produced by the method described above, the storage stability of the composition may be significantly deteriorated. Therefore, a solvent that does not dissolve the encapsulating polymer and dissolves the catalyst It is preferable to wash the microcapsules. If water is used as the continuous phase of the emulsion in which the encapsulating polymer is precipitated, a surfactant or emulsifier may be added to the water to facilitate emulsion formation. The surfactant must not react with the catalyst or inhibit its activity.

The microencapsulated catalyst obtained as described above is isolated from other components of the composition until the composition is heated to the melting point or softening point of the thermoplastic polymer enclosing the catalyst. It is characterized by long-term stability, but relatively rapid hardening at temperatures above the melting or softening point of the thermoplastic polymer. Furthermore, compared to silicone addition type systems, this organic composition is superior in that the microencapsulated catalyst has good dispersibility and a uniform cured product can be obtained.

Mixing the above (A), (B) and (C) components of the present invention,
When cured, a uniform cured product with excellent deep curability can be obtained without phenomena such as foaming.

The molar ratio of the hydronoryl group in component (A) to the alkenyl group in component (B) is preferably 0.2 to 5.0,
Furthermore, 0.4 to 2.5 is particularly preferable. If the molar ratio is less than 0.2, curing will be insufficient, resulting in only a stiff and weak cured product, and if the molar ratio is greater than 5.0, active hydronolyl groups will remain in the cured product even after curing. Since a large amount remains, cracks, cracks, and voids occur, making it impossible to obtain a uniform and strong cured product. In addition, the amount of catalyst and U7
Although there is no particular limitation, the number of moles of the microencapsulated catalyst is preferably in the range of 10-' to 10-j++ol per mol of alkenyl group in component (B).

It is preferably used in a range of 10-3 to 10-'mol. If the amount is less than 10-" mol, curing will not proceed sufficiently. Also, since hydrosilylation catalysts are generally expensive and corrosive, it is preferable not to use more than 10-1-01 mol.

There are no particular restrictions on curing conditions, but generally from 0°C
200'C, preferably 30-150°C for 10 seconds to 4
It is best to allow time to cure. In particular, at high temperatures of 80 to 150°C, some products can be cured in a short time of about 10 seconds to 1 hour. The properties of the cured product depend on the main chain skeleton, molecular weight, etc. of the components (A) and (B) used, but it can be produced from rubber-like to resin-like.

When producing a cured product, in addition to the three essential components (A), (B), and (C), depending on the purpose of use, a solvent, an adhesion improver, a physical property regulator, and a storage stability improver are added. agents, desensitizers, fillers, antiaging agents, ultraviolet absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, amine radical chain inhibitors, phosphorus peroxide decomposers, lubricants, pigments Various additives such as foaming agents and the like can be added as appropriate.

〔Example〕

Hereinafter, the present invention will be explained in more detail based on Examples.
The present invention is not limited in any way by these.

Synthesis Example 1 A 200 d four-loaf flask equipped with a stirring bar, dropping funnel, thermometer, 3-way pot, and cooling tube was prepared. Next, 29.73 g of cyclic hydrogen polysiloxane CH,+ (manufactured by Shin-Etsu Chemical Co., Ltd., LS 8600) was added under a nitrogen atmosphere.
(124 mmol) was charged into the flask. Isophthalic acid diallyl ester (manufactured by Wako Pure Chemical Industries, Ltd.) 9.84
g (40++ mol) and chloroplatinic acid catalyst solvent melt 1n2
PtC], 6H,01,Og in ethanol/1.2-
After dissolving 82 μi of dimethoxy ethyl 7 (1/9 V/V) in 100 d of toluene and mixing well, it was charged into the dropping funnel. 65 flasks
It was heated to ~70°C and the toluene solution was added dropwise over 100 minutes. When the reaction was continued for an additional 1 hour, the 1R spectrum was taken, and the absorption derived from the olefin of 1640C11-' had completely disappeared, so the reaction was terminated at this point. After removing volatile components from the reaction mixture by evaporation, the mixture was dried under reduced pressure at 80°C for 1 hour to obtain 25.85 g of a pale yellow viscous liquid.

This viscous liquid was identified by 300MHz 'IINMR, IR spectrum, etc. as 5i-H having the following structural formula.
It was found that the compound was an ester-based curing agent.

Synthesis Example 2 A 200 d four-loaf flask with a 3-way condenser cooling tube,
Cyclic polyhytronenoloxane CH was prepared in a 6N2 atmosphere using a pressure-equalizing dropping funnel, a thermometer, a magnetic tip, and a glass stopper.

(Manufactured by Shin-Etsu Chemical, LS 8600) 12.03 g
(50smo1) and 20+d of toluene were charged into the flask.

1.9-decadiene 2-16 g (20 mmol)
, chloroplatinic acid catalyst solution ([(zPtcIa -6HzO
Ig to 1g of ethanol, 9g of 1,2-dimethoxoethane
solution dissolved in g) 20μ! was dissolved in 30d of toluene and charged into the dropping funnel.The flask was heated to 50°C.
The flask was placed in an oil bath, and the toluene solution was dropped into the flask over a period of 2 hours under an N2 atmosphere. 50 minutes after completion of dripping
After reacting for an additional hour at °C, the IR spectrum was measured and the olefin absorption near 1640 cm-' had completely disappeared, so the reaction was terminated at this point. After the reaction, the toluene solution was mixed with ammonium chloride saturated aqueous solution (100dX2) and exchanged water (100dX2).
After washing with 1), it was dried with NazSOa. NazSOa
was removed by filtration, volatile components were removed by evaporation, and 9.11 g of a colorless and transparent liquid was obtained by degassing under reduced pressure at 80°C. The hydrosilyl group in the hydrocarbon compound was confirmed as a strong absorption of 2170c+a-'.

Also 300M112 NMI? 5i-H peak and 5
By comparing the intensity ratio of protons with iCH3 (actual value 0.216) and the calculated intensity ratio, the compound has an average structure of the following formula (n-1 (MW-998) is 53%, n = 2 (MW = 1377) was found to be a 47% mixture. Based on this, the number of 5i-H groups per unit weight was calculated to be 0.769 m.

It was 1/100g.

Synthesis Example 3 Bisphenol Al 14 g (0.5 m.1), 5
Sodium hydroxide aqueous solution 250d (1,25mol
) and 515d of ion-exchanged water were thoroughly mixed. Next, hensyltriethylammonium chloride was added as a phase transfer catalyst. 242 g of allyl bromide (2,0
A solution prepared by dissolving mol) in 300 d of toluene was gradually dropped from the dropping funnel. The reaction was carried out at 80°C for 2 hours with stirring. At this point, when we measured the pH of the aqueous layer, it was acidic, so we stopped heating and stirring, washed the organic layer with 0 sodium bicarbonate water, and then washed it with ion-exchanged water.
It was dried. After removing volatile matter with evaporation resin,
By drying under reduced pressure at 80°C for 2 hours, 146 g (yield: 95%) of a pale yellow viscous liquid was obtained. This viscous liquid was identified as diallyl ether CH of bisphenol A by force analysis, 300 MNz 'H NMR, and IR spectrum.

CH.

It was confirmed that

IR(neat) cm-', 3070 (m, v
=c-s), 3030 (m) 2960 (S),
2920 (S), 2860 (S) (ν.-□
), 1645 (m, νc+c), 1620
(S), 1520 (S), 1290 (S)1
235 (S), 1180 (S), 1025 (
S), 1000 (S), 920 (S) 825
(S) Elemental analysis, calculated value C, 1111, 78χ, )I, 7.
84χ Actual Measurement Direct C, 81,9χ ; H, 7,96χ Synthesis Example 4 A 200 d four-loaf flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way pot, and a cooling tube was prepared. Next, in a nitrogen atmosphere, 12.03 g of cyclic hydrogen polysiloxane H3 (manufactured by Shin-Etsu Chemical Co., Ltd., LS 8600) was added.
(50 mmol) and Toluyun 20 were placed in a flask.

Bisphenol A diallyl ether 6.16 g (20 mn+ol) synthesized in Synthesis Example 3, 120 i of chloroplatinic acid catalyst solvent solution (HzPtcI6.6), and Og were dissolved in ethanol/12-dimethoquinoethane (1/9 ν).
/V) 41 μp dissolved in 9 g of toluene 50
After dissolving and mixing thoroughly, the mixture was poured into the dropping funnel. The toluene solution was added dropwise into the flask at 70°C over 1.5 hours. After further reaction at 80°C for 5 hours, an rR spectrum was taken, and the result was 1645 cm-
The reaction was terminated at this point since the absorption derived from the olefin ' had completely disappeared. Evaporate the reaction mixture.
- Plan to remove volatile components, add 100I11 hexane to the residue, dissolve completely, and filter.

The catalyst was removed. I 2. By distilling hexane under reduced pressure and drying under reduced pressure at 80°C for 1 hour. A pale yellow viscous liquid of Og was obtained. This viscous liquid has a frequency of 300MHz
Identification by HNMR and IR spectra revealed that it was a 5i-H-containing ether compound having the following structural formula.

Synthesis example 5 200d! A four-hole flask was equipped with a cooling tube with a three-way stopper, a pressure-equalizing dropping funnel, a thermometer, a magnetic knob, and a glass stopper. Cyclic polyhydrodiene siloxane ")-] Hi (manufactured by Shin-Etsu Chemical, LS 8600) 12.03 g under N2 atmosphere
(50 vof) and 20 m of toluene were charged into the flask.

Diethylene glycol diallyl carbon-1・CH2=
CH-CHz-OCO(CHzCHzO)z-Go-C
Hz-CH2CHz (RAV-7N, manufactured by Mitsui Petrochemical ■) 5.49 g (20-mol), chloroplatinic acid catalyst solution (
1 g of HfPtC16'6Hz0, 1 g of ethanol, 1
．． Solution dissolved in 9g of 2-dimethoxyethane) 41μr
was dissolved in 50 d of toluene and charged into the dropping funnel. The flask was placed in an oil bath at 50°C, and the toluene solution was dropped into the flask over a period of 15R under an N2 atmosphere. When the IR spectrum was measured after the dropwise addition was completed, the absorption of S1/Fin near 1640 cm-' had completely disappeared, so the reaction was terminated at this point. The reaction mixture was evaporated to remove volatile components, yielding 10.2 g of a slightly viscous pale yellowish liquid. The hydrosolyl group of the carbonate compound has an IR spectrum of 21
This was confirmed as strong absorption of 70C11-'. 30 again
By comparing the proton intensity ratio between the peak of 31 and 5iCHx (actual value 0.181) in 0 MHz NMR with the calculated intensity ratio, it was found that the compound has the structure of the following formula on average. Ta. Based on this, the number of 5i-H groups in the unit weight is calculated to be 0.47 mol/1
It was 00g.

Synthesis Example 6 According to the method disclosed in JP-A-53-134095,
Polyoxypropylene having an allylic olefin group at the end was synthesized.

Polyoxypropylene glycol having an average molecular weight of 3000 and powdered caustic soda were stirred at 60°C, and bromochloromethane was added to carry out a reaction to increase the molecular weight.

Next, allyl chloride was added to allyl etherify the terminals at 110''C. This was treated with aluminum silicate to synthesize purified polyoxypropylene with allyl etherified terminals.

The average molecular weight of this polyether was 7960, and 92% of the terminals were olefin groups based on the iodine value. The viscosity measured by an E-type viscometer was 130 boids (40°C).

Synthesis Example 7 300g (0.1 mol) of terminal hydroxyl group polycaprolactone (number average molecular weight 3000, hydroxyl group equivalent 1500), 2
4.0 g of pyridine and 300 d of THF were placed in a round bottom flask equipped with a stirring bar, thermometer, dropping funnel, nitrogen blowing tube, and cooling tube, and 32 g of allyl chloroformate was gradually added dropwise from the dropping funnel at room temperature. . Thereafter, the mixture was heated to 50°C and stirred for 3 hours. After removing the generated salt by filtration 1
Allyl-terminated polycaprolactone was obtained by adding toluene from 50 companies, washing with 200 d of hydrochloric acid aqueous solution, neutralizing, and concentrating. The number average molecular weight of the obtained oligomer was found to be 3,200 by PO measurement. 300MHz NMR
The introduction of an allyl group was confirmed from the spectrum of the olefin portion of . Furthermore, it was confirmed from the quantitative determination of the olefin by iodometric titration that an average of 2.0 allylic unsaturated groups were introduced into each molecule.

Synthesis Example 8 Toluene 5 (ld
was added and dehydrated by azeotropic degassing. A solution of 48 g of t-BuOK in 200 d of THF was injected. After reacting at 50°C for 1 hour, allyl chloride 471f was
It was added dropwise over 0 minutes. After the dropwise addition was completed, the reaction was carried out at 50°C for 1 hour. After the reaction was completed, 30 g of aluminum silicate was added to the reaction solution in order to adsorb the produced salt, and the mixture was stirred at room temperature for 30 minutes. By filtration and purification, about 250 g of allyl-terminated hydrogenated polyisoprene was obtained as a viscous liquid. 300MHz
'HNMR analysis confirmed that allyl groups were introduced into 92% of the ends. The number of moles of olefin determined from the iodine value was 0.1072++ol/100g. Also, the viscosity measured by an E-type viscometer was 302 boids (32
℃).

Typical physical properties of Naeball (from technical data) Hydroxyl group content (eq/g) 0.90 Viscosity (poise)
/30℃) 700 average molecular weight (vpo measurement)
2500 Synthesis Example 9 A 1i four-bottle flask equipped with a stirring bar, dropping funnel, thermometer, 3-way pot, and cooling tube was prepared. Next, 20d of toluene was charged under a nitrogen atmosphere, and 115.72g of n-butyl acrylate was prepared. , Oriru Methacrylate 20.1
6g, n-dodecylmercaptan 6.46g, azobisisobutyronitrile 2.0g, toluene 400IIl
A toluene solution of the following monomers was added dropwise from the dropping funnel over about 1 hour while the toluene was refluxed. After the dropwise addition was completed, the reaction was continued for an additional 2 hours. The toluene solution was treated with aluminum silicate and then suction filtered using a filter aid (diatomaceous earth) to obtain a transparent solution. This solution was evaporated and further dried under reduced pressure at 80'C for 3 hours to obtain about 195 g of a pale yellow viscous liquid oligomer. The number of moles of allyl groups in the polymer determined by iodometric titration was 0.0818 mol/100 g, and the molecular weight determined by VPO was 2950.

From the molecular weight and the number of moles of allyl group determined by iodometric titration,
It was found that on average about 2.4 allyl groups were introduced into one molecule of the polymer.

Synthesis Example 10 2! Equipped with a stirring bar, dropping funnel, thermometer, 3-way pot, and cooling tube! A paraple flask was prepared. First, 7.5 g of polyvinyl alcohol (manufactured by Nippon Gosei Kagaku Kogyo ■, trade name Gohsenol CH20M) dissolved in 30C1d of water was charged into a reactor in a nitrogen stream, and then chloroplatinic acid and tetramethyldivinylsiloxane were reacted. A mixture of 1.33 g of a platinum compound and 14.0 g of polystyrene (manufactured by Asahi Kasei Kogyo ■, trade name Styron) was mixed with 1 part of methylene chloride.
50d was added dropwise over about 15 minutes.

After that, 1000 d of water! and 7 hours at room temperature, 45
Stirred at °C for 12 hours. After the reaction was completed, the mixture was subjected to i4 condensation by centrifugation and filtration to obtain purified microcapsules. After washing this with methanol, it was dried in a vacuum dryer at room temperature for 5 hours to obtain 5.0 g of purified microcapsules. The obtained microcapsules were colorless solids in the form of fine powder, and as a result of elemental analysis using a CHN recorder and platinum analysis using atomic absorption spectroscopy, they were found to be 90% polystyrene and 320% platinum.
It was found to contain 10% of platinum compounds corresponding to ppm+.

Example 1 In order to investigate the compatibility between the 5i-H group-containing ether curing agent produced in Synthesis Example 4 and various allyl group-containing organic polymers having a beaded chain skeleton, the combinations shown in Table 1 were used. A predetermined amount of the curing agent and 1.0 g of the organic polymer were thoroughly mixed, and after centrifugal defoaming, the mixing state was observed. Although some were slightly cloudy, they were generally transparent and uniform. It was found that the 1si-H-containing ether compound has good compatibility with various organic polymers.

Next, in order to examine the curability, each of the above mixtures was added to Synthesis Example 10.
A predetermined amount of the microencapsulated hydrosilylation catalyst prepared in step 1 was added and mixed well. A portion of the mixture was placed on a gelling tester (manufactured by Nissin Scientific Co., Ltd.), and the snap-up time (time until it becomes rubber elastic) was measured at a predetermined temperature. The results are shown in Table 1, and it was found that the composition had fast curing properties at high temperatures.

Table 1: Compatibility and curability of 5i-HJJ-containing ether compounds and allyl group-containing organic polymers (Note 1) (Note 2) The molar ratio of hydrosilyl groups and allyl groups is 1/1. Hydrosilyl group-containing compound of Synthesis Example 4 and Synthesis Examples 6 to 9
The polymer was weighed out.

The microencapsulated catalyst was added so that pt was I x 10-'mol relative to the allyl group of each polymer.

Example 2 The 5i-H base produced in Synthesis Examples 1.2.4 and 5 was mixed with predetermined amounts of various compounds, the ether polymer produced in Synthesis Example 6, and the microencapsulated catalyst synthesized in Synthesis Example IO. 2
The mixture was thoroughly stirred and mixed in the proportions shown in the table. The mixture was degassed by centrifugation and poured into a polyethylene mold. After degassing again at room temperature and under reduced pressure, a uniform rubber-like cured product with a thickness of about 3 mm was obtained by curing at 100°C for 1 hour. JIS K 6301 from the sheet of the cured product
Punch out No. 3 dumbbells that comply with the standards and pull speed 200m+
A tensile test was conducted at s/ll1in. The results are shown in Table 3.

Table 2: Tensile properties of cured product Example 3 9.54 g of allyl group-containing polypropylene oxide produced in Synthesis Example 6, 0.39 g of SIH group-containing ether compound produced in Synthesis Example 4 (allyl group and 5i- (H groups in a molar ratio of 1:1) and 0.15 g of the microencapsulated catalyst obtained in Synthesis Example 10 were thoroughly mixed. After degassing the mixture by centrifugation, it was poured into a mold having a length of 6C11, a width of 0.8 cm, and a depth of 1.81 mm. After defoaming again at room temperature under reduced pressure, by curing at 100'C for 30 minutes,
A rubber-like cured product with a thickness of 13 ml was obtained. JIS K63
When the hardness was measured by the hardness measuring method specified in Section 015-2 Spring Type Hardness Test (Type A), the hardness was 21 on the front surface of the cured product and 22 on the back surface, and a sample with good deep hardenability was obtained.

Example 4 Allyl group-containing hydrogenated polyisoprene 6 produced in Synthesis Example 8
, 00 g, 0.96 g of the 5i-H group-containing ether compound produced in Synthesis Example 4 (molar ratio of allyl group to 5t-H group is 1=1) and the microencapsulated catalyst obtained in Synthesis Example 10. 0.42 g was mixed well. This composition was stored at room temperature, and its viscosity was measured using an E-type viscometer to examine its storage stability. Table 3 shows the results.

Table 3 = Storage stability of one-component composition A uniform cured product can be obtained that is quick-curing and has excellent deep-curing properties.

-Cmo2゛　÷- ’;;=−−,”.

(However, the viscosity was measured at 40°C.) Comparative Example 1 Instead of the microencapsulated catalyst used in Example 4, a chloroplatinic acid catalyst (1, PtC1a・6Hz01g was C)I
, dissolved in 1 m OH and 9 m dimethoxyethane)
3.2μ! When the mixture was prepared and left at room temperature, it turned into a gel two days later. This indicates that the composition using the microencapsulated catalyst has high storage stability. It has been certified.

〔Effect of the invention〕

Claims (1)

[Claims] 1. A curable composition comprising the following components (A), (B) and (C) as essential components; (A) a polymer containing at least two hydrosilyl groups in the molecule; (B) an organic compound containing at least one alkenyl group in the molecule and having a molecular weight of 500 to 5;
(C) Microencapsulated hydrosilylation catalyst. 2. The composition according to claim 1, wherein the organic polymer as component (A) is a compound having a group selected from the following group; A group selected from OSi(CH_3)_3 and a hydrocarbon group having 1 to 10 carbon atoms, and each R may be the same or different. m is a positive integer,
n, p, q are 0 or positive integers, and 1≦m+n+p+
q≦50) Or, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (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) 3. 2. The composition according to claim 1, wherein the organic compound as component (A) is a compound having a group selected from the following group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula , p is a positive integer, q is 0 or a positive integer, and 2≦p+q≦4, R is a group selected from H, OSi(CH_3)_3, and a hydrocarbon group having 1 to 10 carbon atoms. , each R may be the same or different.) 4. The organic polymer of component (B) has the formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 The composition according to claim 1, which is a compound having at least one alkenyl group represented by hydrogen or methyl group. 5. The composition according to claim 1, wherein the catalyst in the form of fine solid particles or fine droplets is encapsulated in microcapsules in which component (C) is made of a thermoplastic organic polymer. 6. The thermoplastic organic polymer is derived from at least one ethylenically unsaturated organic compound or from a condensation reaction between at least two organic compounds containing a plurality of condensable groups per molecule. Item 5. The composition according to item 1 or 5. 7. Claim 6, wherein the ethylenically unsaturated organic compound is selected from the group consisting of ethylenically unsaturated hydrocarbons, acrylonitrile, and esters of acrylic acid or methacrylic acid.
The composition described in . 8. The composition according to claim 1, 5 or 6, wherein component (C) is obtained by precipitating a previously produced thermoplastic organic polymer in the presence of a catalyst in the form of fine droplets or fine solid particles. thing. 9. The composition according to claim 1, wherein the molar ratio of the hydrosilyl group in component (A) to the alkenyl group in component (B) is 0.2 to 5.0. 10. A claim in which the amount of the microencapsulated hydrosilylation catalyst of component (C) is in the range of 10^-^1 to 10^-^■ mole per mole of alkenyl group in component (B). 1. The composition according to item 1.