JP3040143B2 - Curable composition with excellent storage stability - Google Patents

Description

The present invention relates to a curable composition, and more specifically, to (A)
An organic polymer having at least two hydrosilyl groups in the molecule, (B) an organic compound having at least one alkenyl group in the molecule, (C) a hydrosilylation catalyst, and (D) a storage stability improver. The present invention relates to a curable composition having excellent storage stability as an essential component.

[Conventional technology and problems]

Conventionally, various curable liquid compositions which are cured to generate a rubber-like substance have been developed. Above all, as a curing system having excellent deep curing properties, polyorganosiloxanes having an average of two or more vinyl groups in one molecule at the terminal or in the molecular chain, and hydrogen atoms bonding to silicon atoms in one molecule. A crosslinkable polyorganohydrogensiloxane having two or more polyorganohydrogens has been developed, and is used as a sealing agent and a potting agent by utilizing its excellent weather resistance, water resistance and heat resistance. However, this system is limited in its use due to its high cost, poor adhesion, and easy mold generation. Furthermore, the above-mentioned polyorganosiloxane generally has poor compatibility with an organic polymer, and even if an attempt is made to cure a polyorganohydrogensiloxane and an organic polymer containing an alkenyl group, the polyorganosiloxane is phase-separated. The hydrolysis and dehydrocondensation reaction of the compound are promoted, and there is a problem that sufficient mechanical properties cannot be obtained due to voids.

[Means for solving the problem]

The present invention solves these problems as a result of intensive studies in view of such circumstances, and provides a cured product that is fast-curing, and has excellent mechanical properties as well as excellent deep-curing properties.
Another object of the present invention is to provide a curable composition having excellent storage stability. That is, instead of the polyorganohydrogensiloxane conventionally used in the curing reaction by hydrosilylation, an organic polymer containing at least two hydrosilyl groups in the molecule is used, and a polyorganosiloxane containing a vinyl group is used. Instead, if an organic compound containing a non-polymer containing an alkenyl group is used, the compatibility between the two is generally good. Therefore, if the two components are cured using a hydrosilylation catalyst, a uniform curable composition having excellent mechanical properties such as rapid curing and deep curing properties and sufficient tensile properties can be obtained. Also, since it is possible to use Si-H group-containing organic polymers having all kinds of main chain skeletons, it is possible to prepare a cured product applicable to a very wide range of applications, and further by blending a storage stability improver, The present inventors have found that a curable composition having excellent storage stability can be obtained, and have reached the present invention.

That is, the present invention provides the following components (A), (B) and (C)
And (D) as an essential component, and a curable composition having excellent storage stability.

(A) A hydrosilyl group-containing polymer having at least two hydrosilyl groups represented by the following formula (1) in the molecule.

^{X-R 1 - (1)} ( wherein, X is a substituent containing at least one hydrosilyl group, R ¹ is a hydrocarbon group having 2 to 20 carbon atoms, optionally containing one or more ether bonds . or) (B) shown in any one of the following formulas (2) to (5), at least to one chromatic alkenyl groups in a molecule, organic compounds that are not polymeric, ^{_{[H 2 C = C (R 2}} ) - _{^{R 3 -O a R 4 (2}} ) ^{_{[H 2 C = C (R 2}} ) -R 3 -OC (O) a R 5 (3) ^{_{[H 2 C = C (R 2}} a R 6 (4) [ ^{_{H 2 C = C (R 2}} ) -R 3 -OC (O) O a R 7 (5) ( wherein 2 of R ² is hydrogen or a methyl group .R ³ to 20 carbon atoms
The monovalent hydrocarbon group may contain one or more ether bonds. R ⁴ and R ⁵ are an aromatic or aliphatic 1 to 4 valent organic group having 1 to 30 carbon atoms. R ⁶ is a monovalent to tetravalent hydrocarbon group having 2 to 50 carbon atoms. R ⁷ is an aromatic or aliphatic 1 to 4 valent organic group having 1 to 30 carbon atoms. a is an integer selected from 1 to 4. (C) hydrosilylation catalyst, (D) storage stability improver.

The component (A) of the present invention is an organic polymer containing at least two hydrosilyl groups represented by the following formula (1) in the molecule.

X—R ¹ — (1) (X is a substituent containing at least one hydrosilyl group,
R ¹ is a divalent hydrocarbon group having 2 to 20 carbon atoms and may have one or more ether bonds. The substituent containing at least one hydrosilyl group is not particularly limited, but a specific example of a group containing a hydrosilyl group is -Si (H) _n (CH ₂ ) _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) hydrosilyl group containing only one silicon atom, such _{as, -Si (CH 3) 2 Si} (CH 3) 2 H, -
_{Si) CH 3) 2 CH 2} CH 2 Si (CH 3) 2 H, -Si (CH 3) 2 SiCH 3 H 2, _{-Si (CH 3) 2 NHSi (} CH 3) 2 H, -Si (CH 3) 2 N [Si (CH 3)
₂ H] ₂ , A group containing two or more silicon atoms, such as (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 ≦ 5
0) (R, m, n are the same as above) (Where R is the same as above, m is a positive integer, n, p, q are 0 or positive integers, and 1 ≦ m + n + p + q ≦ 50) (Wherein, R is the same as above, m is a positive integer, n is 0 or a positive integer, and 2 ≦ m + n ≦ 50) Various chain, branched, and cyclic polyvalent hydrogens represented by And groups derived from siloxane.

Among the above various hydrosilyl group-containing groups, from the viewpoint that the compatibility of the hydrosilyl group-containing organic compound of the present invention with various organic polymers is less likely to be impaired, the molecular weight of the group constituting the hydrosilyl group is 500. The following is desirable, and considering the reactivity of the hydrosilyl group,
The following are preferred.

(Where R is the same as above, m is a positive integer, n, p, and q are 0
Or a positive integer and 1 ≦ m + n + p + q ≦ 50) For example, (Where p is a positive integer, q is 0 or a positive integer, and 2 ≦ p + q ≦ 4) When two or more hydrosilyl-containing groups are present in the same molecule, they may be the same or different.

The total number of hydrosilyl groups contained in the organic polymer (A) may be at least two in one molecule, but is preferably 2 to 15, and particularly preferably 3 to 12. When the hydrosilyl group-containing organic curing agent of the present invention is mixed with various organic polymers containing an alkenyl group in the presence of a hydrosilylation catalyst and cured by a hydrosilylation reaction, the number of hydrosilyl groups is preferably less than 2. If the amount is too small, the curing is slow and often causes poor curing. When the number of the hydrosilyl groups is more than 15, the stability of the curing agent deteriorates, and a large amount of the hydrosilyl groups remains in the cured product even after curing, which causes voids and cracks.

The component (A) has a hydrosilyl group bonded to an organic polymer in the form represented by the above formula (1). As the organic polymer, those having various main chain skeletons can be used.

First, as the polyether polymer, for example, polyoxyethylene, polyoxypropylene, polyoxytetramethylene, a polyoxyethylene-polyoxypropylene copolymer, or the like is suitably used. Other polymers having a main chain skeleton include polyester polymers, ethylene-propylene copolymers obtained by condensation of dibasic acids such as adipic acid and glycol or ring-opening polymerization of lactones,
Polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, copolymers of isoprene with butadiene, acrylonitrile, styrene, etc., copolymers of polybutadiene, butadiene with styrene, acrylonitrile, etc., polyisopyrene, polybutadiene , Polyolefin-based polymers obtained by hydrogenating copolymers of isoprene or butadiene with acrylonitrile, styrene, etc., polyacrylates, ethyl acrylate, butyl obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate Acrylic esters such as acrylates and vinyl acetate,
Acrylonitrile, methyl methacrylate, acrylate copolymers with styrene, etc., a graft polymer obtained by polymerizing a vinyl monomer in the organic polymer,
Polysulfide-based polymer, nylon 6 by ring-opening polymerization of ε-aminocaprolactam, nylon 66 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 610 by condensation polymerization of hexamethylenediamine and sebacic acid,
Nylon 11, ε by condensation polymerization of ε-aminoundecanoic acid
Nylon 12 by ring-opening polymerization of aminolaurolactam,
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 from bisphenol A and carbonyl chloride, diallyl phthalate-based polymers, etc. Is exemplified.

The hydrosilyl group-containing organic polymer as the component (A) is
It may be linear or branched, and any one having a molecular weight of 500 to 50,000 can be suitably used, and one having a molecular weight of 500 to 20,000 is particularly preferred. The hydrosilyl group of the component (A) may be at the molecular terminal or in the molecule. However, when a rubber-like cured product is produced using the composition of the present invention, the effective network is preferably located at the molecular terminal. It is preferable because the chain length becomes long.

There is no particular limitation on the method for producing the component (A), and any method may be used. For example, (i) Si—
A method in which an organic compound having a Cl group is treated with a reducing agent such as LiAlH ₄ or NaBH ₄ to reduce the Si—Cl group in the compound to a Si—H group, (ii) having a functional group X in the molecule A method of reacting an organic compound with a compound having a functional group Y and a hydrosilyl group simultaneously reacting with the above functional group in the molecule, (iii) at least 2
A method of selectively hydrosilylating a polyhydrosilane compound having two hydrosilyl groups so that the hydrosilyl group remains in the molecule of the compound even after the reaction can be considered. Of these, the method (iii) is particularly preferred.

The non-polymeric organic compound containing at least one alkenyl group in the molecule as the component (B) of the present invention includes a compound represented by the formula (6): Wherein R ² is hydrogen or a methyl group.

More specifically, first, equation (2) (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. R ⁴ is an organic group having 1 to 30 carbon atoms. And a is an integer selected from 1 to 4.) and a compound having an ether bond represented by the following formula:

In the formula (2), R ³ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ³ may contain one or more ether bonds. Specifically, -CH _2- , -CH ₂ CH ₂
−, −CH ₂ CH ₂ CH ₂ −, _{-CH 2 CH 2 O-CH 2} CH 2 -, - CH 2 CH 2 O-CH 2 CH 2 CH 2 - and the like. —CH ₂ — is preferred from the viewpoint of ease of synthesis.

In the formula (2), R ⁴ is an aromatic or aliphatic monovalent to tetravalent organic group having 1 to 30 carbon atoms. Specifically, CH
₃ −, CH ₃ CH ₂ −, CH ₃ CH ₂ CH ₂ −, (N is an integer of 2 to 10). Of these, the following are preferred.

Next, the general formula (3) (R ² is hydrogen or a methyl group, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ⁵ is an organic group having 1 to 30 carbon atoms. , A is an integer selected from 1 to 4.).

In the formula (3), R ³ is the same as R ³ in the formula (2).
R ⁵ is a C 1-30 aromatic or aliphatic C 1-4
Is a valence organic group. Specifically, And the like. Of these, the following are preferred.

-(CH ₂ ) ₂ -,-(CH ₂ ) ₃ -,-(CH ₂ ) _6- , Next, the general formula (4) Wherein R ² is hydrogen or a methyl group, R ⁶ is a monovalent to tetravalent hydrocarbon group having 2 to 50 carbon atoms, and a is an integer selected from 1 to 4. Is mentioned.

In the formula (4), R ⁶ represents a monovalent to tetravalent hydrocarbon group having 2 to 50 carbon atoms. Further, — (CH ₂ ) _n — (n = 2 to 10) is particularly preferred.

As a specific example of the component (B), a compound represented by the general formula (5) (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. R ⁷ is an aromatic group having 1 to 30 carbon atoms. System or aliphatic system 1-4
A is an integer selected from 1 to 4. And a compound having a carbonate bond represented by the formula:

Wherein, R ³ is the formula (2), which is the same as R ³ in (3). As R ⁷ is, (N is an integer of 2 to 10) CH ₂ CH ₂ O) _n CH ₂ CH ₂ − (n is an integer of 1 to 5) CH ₂ CH ₂ CH ₂ O) _n CH ₂ CH ₂ CH ₂ − (n is an integer of 1 to 5) CH ₂ CH ₂ CH ₂ CH ₂ O) _n CH ₂ CH ₂ CH ₂ CH ₂ − (n is 1 to 5) An integer of 5). Of these, the following are particularly preferred.

−CH ₂ CH ₂ OCH ₂ CH ₂ − −CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ − The alkenyl group-containing organic compound as the component (B) may be used alone or as a mixture of two or more.

The alkenyl group-containing organic compound of the component (B) has a molar ratio of the alkenyl group to the hydrosilyl group of the component (A) of 0.1.
It is preferable to use in the range of 2 to 5.0. This is because if the molar ratio is less than 0.2, poor curing occurs, and if it is more than 5.0, mechanical properties after curing are reduced.

Examples of the hydrosilylation catalyst which is the component (C) of the present invention include platinum alone, solid platinum supported on a carrier such as alumina, silica and carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde and ketone. , Platinum-olefin complex {for example, Pt (CH ₂ CHCH ₂ ) _{2
(PPh 3) 2, Pt (} CH 2 = CH 2) 2 Cl 2}; platinum - vinylsiloxane complex {for _{example, Pt n (ViMe 2 SiOSiMe 2} Vi) m, Pt
[(MeViSiO) ₄ ] _m {; platinum-phosphine complex {eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ }; platinum-phosphite complex {eg, Pt [P (OPh ₃ ) ₄ , Pt [ P (OB
u) ₃ ] ₄ ｝ (where 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 platinum-hydrocarbons described in Ashby U.S. Pat. Nos. 3,159,601 and 3,151,662. Also included are the complexes, as well as the platinum alcoholate catalysts described in Lamoreaux, US Pat. No. 3,209,972. Further, the platinum chloride-olefin complex described in Modic U.S. Pat. No. 3,516,946 is also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PP
_{h 3) 3, RhCl 3,} RhlAl 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 or in combination of two or more.
From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex,
Platinum-vinylsiloxane complexes are preferred.

The amount of the catalyst is not particularly limited, but is preferably in the range of 10 ^-1 to 10 ^-8 mol per ¹ mol of the alkenyl group in the component (B). Preferably, it is used in the range of 10 ^-3 to 10 ^-6 mol. If the amount is less than 10 ^-8 mol, 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 cause foaming of the cured product. Therefore, it is preferable not to use the hydrosilylation catalyst in an amount of more than 10 ^-1 mol.

When the hydrosilyl group-containing organic polymer as the component (A) of the present invention is produced by the above-described selective hydrosilylation,
Even after the reaction, since the component (A) contains a hydrosilylation catalyst, its stability is generally not good, and if it is left for a long period of time or if moisture is mixed in, the Si—H group is converted to a Si—OH group. And phenomena such as viscosity increase and gelation are observed. Therefore, it is essential to include a storage stability improver as the component (D) in the component (A). Furthermore, this (D)
The components deactivate the hydrosilylation catalyst at low temperatures,
Since the hydrosilylation reaction is not hindered at a relatively high temperature, the composition of the present invention gives a cured product having excellent mechanical properties.

As the component (D), a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide, and the like can be favorably used.

Compounds containing an aliphatic unsaturated bond include compounds represented by general formula (7): (Wherein R ⁸ and R ⁹ are a hydrogen atom, an alkyl group, an aryl group, or R ⁸ and R ⁹ are interconnected at the other end) represented by the general formula (8) Wherein R ¹⁰ , R ¹¹ , and R ¹² are a hydrogen atom or a hydrocarbon group, and the total number of carbon atoms of R ¹⁰ , R ¹¹ , and R ¹² is 2-6. ^{When 10} , R ¹¹ and R ¹² are hydrocarbon groups, R ¹⁰ and R ¹¹ or R ¹¹ and R ¹² may be mutually connected at the other end.), And the general formula (9) (Wherein R ¹³ , R ¹⁴ and R ¹⁵ are a hydrocarbon group having 1 to 10 carbon atoms, provided that R ¹⁴ and R ¹⁵ may be mutually connected at the other end. ), General formula (10) (Wherein at least one of R ¹⁶ is a hydrocarbon group having an acetylenically unsaturated bond) represented by the general formula (11) (Wherein, R ^{17 to} R ²¹ are a hydrogen atom, a halogen or a monovalent hydrocarbon group, X is a halogen or an alkoxy group such as chlorine or bromine), tetramethylvinylsiloxane cyclic, 2-pentene Nitrile, general formula (12) (Wherein R ²² is a monovalent organic group containing at least one acetylene bond), an aliphatic carboxylic acid ester of an olefinic alcohol such as vinyl acetate,
Formula (13) alkyl dicarboxylate represented by _{^{R 23 O 2 C-C≡C-}} CO 2 R 23 (13) ( wherein, R ²³ is methyl, a hydrocarbon group of ethyl, etc.), the general formula ( 1
Four) (Wherein R ²⁴ is methyl,
Hydrocarbon groups such as ethyl, allyl, and hydrocarbonoxyalkyl group), diorganofumarate and the like.

Triorganophosphine as an organic phosphorus compound,
Examples thereof include diorganophosphine, triorganophosphite, and organophosphonic acid.

Examples of the organic sulfur compound include organomercaptan, diorganosulfide, diorganosulfoxide, organosilanes containing a mercapto group, hydrogen sulfide, benzothiazole, benzothiazole disulfite, 2- (4-
(Morphodinyldithio) benzothiazole and the like.

Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamine, arylamine, alkylarylamine, N, N-diorganoamino alcohol, urea, thiourea, pyrimidine, picoline, hydrazine, sulfonamide, benzotriazole, and quinoline. , Triallyl isocyanurate, a diamine compound represented by the general formula (15) R ²⁵ ₂ NR ²⁷ NR ²⁶ ₂ (15) (where R ²⁵ is an alkyl group containing 1 to 4 carbon atoms, R ²⁶ is hydrogen or R ²⁵ and R ²⁷
Is an alkyl group containing 2 to 4 carbon atoms).

Stannous halide dihydrate as a tin compound,
Examples thereof include stannous carboxylate.

Examples of the organic peroxide include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 2,5-dimethyl-2,5-di (t-butyl). Peroxy) -3-hexyne, dicumyl peroxide, t
-Butylcumyl peroxide, dialkyl peroxides such as α, α'-bis (t-butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl Diacyl peroxides such as peroxides,
Peresters such as t-butyl perbenzoate, diisopropyl percarbonate, peroxydicarbonates such as di-2-ethylhexyl percarbonate, 1,1-di (t-butylperoxy) cyclohexane, 1,1- Examples thereof include peroxyketals such as di (t-butylperoxy) -3,3,5-trimethylcyclohexane.

Among them, dialkyl malate, dialkyl acetylenedicarboxylate, 2-pentennitrile, benzothiazole, quinoline, 2, 3-Dichloropropene is preferred. Further, 2-pentenenitrile, benzothiazole, and quinoline are particularly preferable because the viscosity increase of the component (A) is almost completely suppressed even at a relatively high temperature (about 50 ° C.).

The amount of the component (D) can be almost arbitrarily selected as long as it is uniformly dispersed in the organic polymer of the component (A) and the component (B). It is preferably used in the range of 10 ^-5 to 10 ^-1 mol. This is because if it is less than 10 ^-5 mol, the storage stability of the component (A) is not sufficiently improved, and if it exceeds 10 ^-1 mol, curing is inhibited. The storage stability improver of the component (D) may be used alone or in combination of two or more.

The composition of the present invention is not limited in its storage form except that the component (D) is contained in the component (A). For example, since the component (D) not only improves the storage stability of the component (A) but also has a function of delaying the curing by the addition reaction of the components (A) and (B), the composition of the present invention It is also possible to make one package. But,
In terms of long-term storage stability, for example, (A)
It is more preferable to form a two-package composition in which the component and the component (D) and the component (B) and the component (C) each constitute one package. If it is packaged, it is preferable to store it at a low temperature (0 ° C. or lower).

If the components (A) and (C) containing the component (D) of the present invention are mixed and cured, a uniform cured product having excellent deep curability can be obtained. The curing conditions are not particularly limited, but it is generally preferable to cure at 20 to 200 ° C., preferably 50 to 150 ° C., for 10 seconds to 4 hours. Particularly, at a high temperature of 80 to 150 ° C., a composition which cures in a short time of about 10 seconds to 1 hour can be obtained.

Foaming may be observed at the stage of curing the composition, but foaming can be suppressed by adding a transition metal powder such as iron, cobalt, nickel, copper, or tungsten to the composition. Foaming can also be suppressed by mixing the components (A) to (D) at a low temperature (−60 to 5 ° C.) and curing at a relatively low temperature (25 to 100 ° C.).

The properties of the cured product depend on the main chain skeleton, molecular weight, etc. of the components (A) and (B) used, but can be prepared from rubbery to resinous.

When preparing a cured product, in addition to the essential four components (A), (B), (C), and (D), a solvent, an adhesion improver, a physical property modifier, and a storage agent are used depending on the purpose of use. Stability improvers, plasticizers, fillers, antioxidants, ultraviolet absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, amine radical chain inhibitors, phosphorus peroxide decomposers, lubricants And various additives such as a pigment and a foaming agent can be appropriately added.

The cured product of the present invention can be applied to various uses. For example, adhesives / adhesives, paints, paint waterproofing agents,
Foam sealing agents, potting agents for electric / electronic use, films, cosmetics, molded articles for medical use, dental impression agents, etc.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1 According to the method disclosed in JP-A-53-134095, polyoxypropylene having an allyl-type olefin group at a terminal 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, and the terminal was allyl etherified at 110 ° C. This was treated with aluminum silicate to synthesize a purified terminal allyl etherified polyoxypropylene.

The average molecular weight of this polyether was 7,960, and 92% of the terminals were olefin groups based on the iodine value. The viscosity measured by an E-type viscometer was 130 poise (40 ° C.).

Synthesis Example 2 A 14-neck flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a condenser was prepared. Next, under a nitrogen atmosphere, the cyclic polysiloxane 41.7 g (0.173 mol) (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged in the flask. The terminal 92 of the molecule synthesized in Synthesis Example 1
% Polypropylene oxide 300g an allyl group (number of moles 0.069mol allyl group), toluene 230 ml, and chloroplatinic acid catalyst solvent chloride _{(H 2 PtCl 6 · 6H 2} O 1g of ethanol 1 ml, 1, 2
A solution of 83 μl of toluene dissolved in 9 ml of dimethoxyethane was charged into the dropping funnel. The flask
The mixture was heated to 70 ° C., and the toluene solution was added dropwise at a rate of about 2 ml per minute over 5 hours. Thereafter the reaction temperature at the time of stirring up to about 6 hours 80 ° C., where the remaining allyl groups in the reaction solution was determined by IR spectroscopy, 1645 cm ^-1
It was confirmed that the carbon-carbon double bond had disappeared. Further, in order to remove toluene and unreacted excess cyclic polysiloxane in the reaction system, vacuum degassing was performed at 80 ° C. for 3 hours, and about 315 g of hydrosilyl group-containing polypropylene oxide was obtained as a pale yellow viscous liquid. Obtained. The viscosity measured by an E-type viscometer was 310 poise (40 ° C.). The hydrosilyl group in the polypropylene oxide was confirmed as a strong absorption at 2150 cm ^{-1 in} the IR spectrum. 300MHz NM
By analyzing the R spectrum and comparing the peak intensity of the combined Si—CH ₃ and Si—CH ₂ — with the peak intensity of Si—H, an average of 1.31 hydrosilyl groups per molecule of the cyclic polysiloxane was obtained. Was found to have reacted. That is, the polymer is a polypropylene oxide having a molecular terminal represented by the following formula and having a molecular weight partially increased by the cyclic hydrogen polysiloxane.

Synthesis Example 3 300 g (0.1 mol) of terminal hydroxyl group polycaprolactone (number-average molecular weight 3000, hydroxyl equivalent 1500), 24.0 g of pyridine, 300 ml of THF were equipped with a stirring rod, a thermometer, a dropping funnel, a nitrogen blowing tube, and a cooling tube. Into a round bottom flask
At room temperature, 32 g of allyl chloroformate was gradually dropped from the dropping funnel. Thereafter, the mixture was heated to 50 ° C. and stirred for 3 hours. After removing the generated salt by filtration, 150 ml of toluene was added, and 200 ml of toluene was added.
Allyl-terminated polycaprolactone was obtained by washing with an aqueous hydrochloric acid solution, neutralization and concentration. VPO measurement of the obtained oligomer showed that the number average molecular weight was 3,200. 300MHz N
The introduction of the allyl group was confirmed from the spectrum of the olefin portion of the MR. Further, from the determination of the olefin by iodine titration, it was confirmed that an average of 2.0 allyl-type unsaturated groups were introduced in one molecule.

Synthesis Example 4 A 300 ml four-necked flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a condenser was prepared. Next, under a nitrogen atmosphere, the cyclic polysiloxane 34.55 g (0.1435 mol) (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged in the flask. 100 g of polycaprolactone having an average of 2.0 allyl groups in one molecule synthesized in Synthesis Example 3
(Moles 0.0575mol olefin), ethanol toluene 100 ml, and chloroplatinic acid catalyst solvent chloride _{(H 2 PtCl 6 · 6H 2} O 1g
Solution dissolved in 1 ml, 9 ml of 1,2-dimethoxyethane) 60
A toluene solution consisting of μ was charged into the dropping funnel.
The flask was heated to 70 ° C. and the toluene solution was added dropwise over about 2 hours. After completion of the dropwise addition, when the mixture was stirred at 80 ° C. for about 5 hours, remaining allyl groups in the reaction solution were quantified by IR spectroscopy. It was confirmed that the carbon-carbon double bond at 1645 cm ⁻¹ had disappeared. Was done. Next, in order to remove the catalyst remaining in the reaction system, 10 g of silica gel (Wako Pure Chemical Industries, Ltd., Wakogel C-200) was added at room temperature, and the mixture was stirred for 2 hours and filtered using a flash column. did. To remove toluene and excess cyclic polysiloxane,
The filtrate was evaporated and further devolatilized under reduced pressure at 80 ° C. for 3 hours to obtain a colorless transparent viscous liquid. The hydrosilyl group in the polycaprolactone was confirmed as a strong absorption at 2150 cm ^{-1 in} the IR spectrum. S at 300MHz NMR spectrum
and Si-CH ₂ and Si-CH ₂ peak of the i-H - by comparing the intensities of the peaks of the combined and, cyclic polysiloxane 1 Average 1.05 hydrosilyl groups per molecule was found to have reacted. That is, the polymer is a polycaprolactone having a molecular terminal represented by the following formula, the molecular weight of which is partially increased by the cyclic hydrogen polysiloxane.

Synthesis Example 5 50 ml of toluene was added to 300 g of hydrogenated polyisoprene having a hydrosilyl group at both terminals (Epol, trade name, manufactured by Idemitsu Petrochemical Co., Ltd.), and the mixture was dehydrated by azeotropic degassing. t-BuOK48
g was dissolved in 200 ml of THF. After reacting at 50 ° C. for 1 hour, 47 ml of allyl chloride was added dropwise over about 30 minutes. After the completion of the dropwise addition, the reaction was carried out at 50 ° C. for 1 hour. After the completion of the reaction, 30 g of aluminum silicate was added to the reaction solution to adsorb the generated salt, and the mixture was stirred at room temperature for 30 minutes. Filtration and purification yielded about 250 g of allyl-terminated hydrogenated polyisoprene as a viscous liquid. 300 MHz 1H NMR analysis confirmed that 92% of the terminal had an allyl group introduced. The number of moles of the olefin determined from the iodine value was 0.1072 mol / 100 g. The viscosity measured by an E-type viscometer was 302 poise (32 ° C.).

* Typical physical properties of Epol (from technical samples) Hydroxyl content (meq / g) 0.90 Viscosity (poise / 30 ℃) 700 Average molecular weight [VPO measurement] 2500 Synthesis Example 6 Stirrer bar, dropping funnel, thermometer 3, A 300 ml four-necked flask equipped with a side cock and a condenser was prepared. Next, under a nitrogen atmosphere, the cyclic polysiloxane 31.5 g (0.131 mol) (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged into the flask. Of the molecular end synthesized in Synthesis Example 5
Hydrogenated polyisoprene 50 g 92% is allyl group (number of moles of olefin 0.0536mol), toluene 50 ml, and chloroplatinic acid catalyst solvent chloride _{(H 2 PtCl 6 · 6H 2} O 1g of ethanol 1 ml, 1, 2
A solution of 60 μl of toluene dissolved in 9 ml of dimethoxyethane was charged into the dropping funnel. The flask
The mixture was heated to 70 ° C., and the toluene solution was added dropwise over about 2 hours. After completion of the dropwise addition, when the mixture was stirred at 80 ° C. for about 5 hours, remaining allyl groups in the reaction solution were quantified by IR spectroscopy. It was confirmed that the carbon-carbon double bond at 1645 cm ⁻¹ had disappeared. Was done. Next, in order to remove the catalyst remaining in the reaction system, silica gel (manufactured by Wako Pure Chemical Industries, Ltd.,
5 g of Wakogel C-200) was added at room temperature, and the mixture was stirred for 2 hours and filtered using a flash column. The filtrate was evaporated to remove toluene and excess cyclic polysiloxane, and further devolatilized under reduced pressure at 80 ° C. for 3 hours to obtain a colorless transparent viscous liquid. The viscosity measured by an E-type viscometer was 514 poise (23 ° C.). The hydrosilyl group in the hydrogenated polyisoprene was confirmed as a strong absorption at 2150 cm ^{-1 in} the IR spectrum. At 300 MHz, an average of 1.2 hydrosilyl groups per molecule of the cyclic polysiloxane was reacted by comparing the intensity of the peak of Si-H with the peak of Si-CH ₃ and Si-CH ₂ -by NMR spectrum. I knew it was done. That is, the polymer is a hydrogenated polyisoprene having a molecular terminal represented by the following formula, the molecular weight of which is partially increased by the cyclic hydrogen polysiloxane.

Synthesis Example 7 A four-necked flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a cooling tube was prepared. Next, 20 ml of toluene was charged under a nitrogen atmosphere. n-butyl acrylate 25.6 g, allyl methacrylate 2.52 g, n-dodecyl mercaptan 0.81 g, azobisisobutyronitrile 1.0
g, a toluene solution of a monomer consisting of 100 ml of toluene,
The mixture was dropped from the dropping funnel over about 1 hour under reflux of toluene. After the completion of the dropwise addition, the reaction was further continued for 2 hours. After treating the toluene solution with aluminum silicate, a filter aid (diatomaceous earth)
An almost transparent solution was obtained by absorption filtration using. This solution was evaporated and further dried under reduced pressure at 80 ° C. for 3 hours to obtain a pale yellow viscous liquid oligomer.
26 g were obtained. The number of moles of allyl groups in the polymer determined by iodine titration was 0.154 mol / 100 g, and the molecular weight determined by VPO was 3,900. From the molecular weight and the number of moles of allyl groups determined by iodine titration, it was found that an average of about 6.0 allyl groups were introduced into one molecule of the polymer.

Synthesis Example 8 A 200 ml four-necked flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a condenser was prepared. Next, under a nitrogen atmosphere, the cyclic polysiloxane 9.26 g (38.5 mmol) (manufactured by Shin-Etsu Chemical Co., Ltd., LS8600) and 20 ml of toluene were charged in a flask. Allyl group-containing acrylate polymer 10g synthesized in Synthesis Example 7, chloroplatinic acid catalyst solvent chloride _{(H 2 PtCl 6 · 6H 2} O 1g of ethanol 1 ml,
A toluene solution in which 16 μm of a solution in which 9 μl of 1,2-dimethoxyethane was dissolved in 30 ml of toluene was charged into a dropping funnel. The flask was heated to 70 ° C. and the toluene solution was
It was dropped into the flask over a period of minutes. After the completion of the dropwise addition, the reaction was further performed at 80 ° C. for 2 hours. At this point, when the remaining allyl groups in the reaction solution were quantified by IR spectrum analysis,
It was confirmed that the carbon-carbon double bond at 1645 cm ^-1 had disappeared. Furthermore, silica gel (Wakogel C-manufactured by Wako Pure Chemical Industries, Ltd.) was used to remove the catalyst remaining in the reaction system.
200) 2 g was added, and the mixture was stirred at room temperature for about 30 minutes, and then filtered using a flash column. Evaporating the filtrate to remove toluene and excess cyclic polysiloxane;
Further, deaeration under reduced pressure was performed at 80 ° C. for 3 hours to obtain a colorless transparent viscous liquid. The hydrosilyl group in the acrylate polymer was confirmed as a strong absorption at 2150 cm ^{-1 in} the IR spectrum. By comparing the intensity of the peak by combining the Si-H peak and Si-CH ₃ and Si-CH ₂ by NMR spectrum of 300MHz also has said cyclic polysiloxane 1 average of about 1.1 hydrosilyl groups per molecule It turned out to have reacted. That is, the polymer is a hydrosilyl group-containing acrylate polymer having a structure as shown in the following formula in which the molecular weight is partially increased by the cyclic hydrogen polysiloxane.

Synthesis Example 9 114 g (0.5 mol) of bisphenol A, 250 ml (1.25 mol) of a 5N aqueous sodium hydroxide solution and 575 ml of ion-exchanged water were mixed well. Next, benzyltriethylammonium chloride is used as a phase transfer catalyst. added. A solution in which 242 g (2.0 mol) of allyl bromide was dissolved in 300 ml of toluene was gradually added dropwise from the dropping funnel to the aqueous solution. The reaction was carried out with stirring at 80 ° C. for 2 hours. At this time, the pH of the aqueous layer was measured and found to be acidic. After washing the organic layer with aqueous sodium bicarbonate, it was further washed with ion-exchanged water and dried over Na ₂ SO ₄ . After removing volatile components by evaporation, the residue was dried under reduced pressure at 80 ° C. for 2 hours to obtain 146 g (95% yield) of a pale yellow viscous liquid. The viscous liquid was identified by elemental analysis, 300 MNz ¹ HNMR, and IR spectrum to identify the diallyl ether of bisphenol A. Was confirmed.

IR (neat) cm ^-1 , 3070 (m, ν = _CH ), 3030 (m), 2960
(S), 2920 (S), 2860 (S) (ν _CH ), 1645 (m, ν
_CC ), 1620 (S), 1520 (S), 1290 (S), 1235 (S),
1180 (S), 1025 (S), 1000 (S), 920 (S), 825
(S) Elemental analysis, Calculated value C, 81.78%; H, 7.84% Measured value C, 81.9%; H, 7.96% Storage stability test (1) Si with polypropylene oxide produced in Synthesis Example 2 as main chain skeleton Various storage stability improvers were added to the -H group-containing polymer in an amount of 30 equivalents relative to platinum, and each was stored at 50 ° C., and the change in viscosity over time was measured. The results are shown in Table 1.

It can be seen that the addition of a stability improver dramatically improves the storage stability of the polymer.

Storage stability test (2) The storage stability of the Si-H group-containing polymer having the main chain skeleton of the hydrogenated polyisoprene produced in Synthesis Example 6 was examined in the same manner as in Example 1. The results are shown in Table 2, and the effect of benzothiazole was the largest.

Example 1 In order to examine the compatibility between the allyl group-containing ether-based compound produced in Synthesis Example 9 and various Si-H group-containing organic polymers having a main chain skeleton, a combination as shown in Table 3 was used. A predetermined amount of the compound and 1.0 g of the organic polymer were mixed well, and after defoaming by centrifugation, the mixed state was observed. Some were slightly cloudy, but generally transparent and uniform. The allyl group-containing ether compound was found to have good compatibility with various organic polymers.

Next, Synthesis Example 2 was applied to each of the above mixtures to examine curability.
A predetermined amount of a solution obtained by diluting the chloroplatinic acid catalyst solution used 10 times in 10 times was added and mixed well. The storage stability improvers described in Table 3 were used. A part of the mixture was taken on a gelling tester (manufactured by Nissin Kagaku Co., Ltd.), and the snap-up time (time until rubber elasticity) was measured at a predetermined temperature. The results are shown in Table 3, and it was found that the composition was quick-curing at high temperatures.

Example 2 A predetermined amount of the Si-H group-containing ether polymer produced in Synthesis Example 2, the ether compound produced in Synthesis Example 9, the ester compound, the hydrocarbon compound, and the polycarbonate compound shown in Table 4 The compound, the chloroplatinic acid catalyst solution used in Synthesis Example 2, and the storage stability improver were mixed well at the ratio shown in Table 4. The mixture was defoamed by centrifugation and poured into a polyethylene mold. By degassing again at room temperature under reduced pressure and then curing at 100 ° C for 1 hour,
A uniform rubbery cured product having a thickness of about 3 mm was obtained. A No. 3 dumbbell compliant with JIS K 6301 was punched from the sheet of the cured product, and a tensile test was performed at a tensile speed of 200 mm / min. The results are shown in Table 5.

From Table 5, it was found that when the curable composition of the present invention was used, it could be cured in a short time to produce a uniform rubber-like cured product.

Example 3 12.0 g of the Si-H group-containing polypropylene oxide produced in Synthesis Example 2, 1.3 g of the allyl group-containing ether compound obtained in Synthesis Example 9 (molar ratio of allyl group to Si-H group is 1) and The same chloroplatinic acid catalyst solution 44 μm used in Synthesis Example 2
And 4 μm of dimethyl acetylenedicarboxylate were thoroughly mixed with stirring. After defoaming the mixture by centrifugation,
It was poured into a 6 cm, 0.8 cm wide, 1.8 cm deep formwork. After defoaming again at room temperature under reduced pressure, the mixture was cured at 100 ° C. for 30 minutes to obtain a rubbery cured product having a thickness of 13 mm. JIS K 6301
The hardness was measured by the hardness measurement method specified in the 5-2 paragraph spring hardness test (A type).
5. The back surface was 26, and a sample having good deep curability was obtained.

〔The invention's effect〕

The use of the composition of the present invention makes it possible to obtain a uniform cured product having good mechanical properties, rapid curability, excellent deep curability, and excellent storage stability.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Makoto Chinami 6-6-6 Maikodai, Tarumizu-ku, Kobe, Hyogo Prefecture 5-12 (72) Inventor Kazuya Yonezawa 5-12-11, Tsutsujigaoka, Tarumi-ku, Kobe, Hyogo (56 References JP-A-1-138230 (JP, A) JP-A-63-35656 (JP, A) JP-A-2-14244 (JP, A) JP-A-1-45468 (JP, A) JP-A-56-20051 (JP, A) JP-A-61-141758 (JP, A) JP-A-62-294239 (JP, A) JP-A-52-132064 (JP, A) JP-A-3-294320 (JP, A) A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (9)

(57) [Claims] 1. A curable composition having excellent storage stability comprising the following components (A), (B), (C) and (D) as essential components. (A) A hydrosilyl group-containing polymer having at least two hydrosilyl groups represented by the following formula (1) in the molecule. ^{X-R 1 - (1)} ( wherein, X is a substituent containing at least one hydrosilyl group, R ¹ is a hydrocarbon group having 2 to 20 carbon atoms, optionally containing one or more ether bonds . or) (B) shown in any one of the following formulas (2) to (5), at least to one chromatic alkenyl groups in a molecule, organic compounds that are not polymeric, ^{_{[H 2 C = C (R 2}} ) - _{^{R 3 -O a R 4 (2}} ) ^{_{[H 2 C = C (R 2}} ) -R 3 -OC (O) a R 5 (3) ^{_{[H 2 C = C (R 2}} a R 6 (4) [ ^{_{H 2 C = C (R 2}} ) -R 3 -OC (O) O a R 7 (5) ( wherein 2 of R ² is hydrogen or a methyl group .R ³ to 20 carbon atoms
The monovalent hydrocarbon group may contain one or more ether bonds. R ⁴ and R ⁵ are an aromatic or aliphatic 1 to 4 valent organic group having 1 to 30 carbon atoms. R ⁶ is a monovalent to tetravalent hydrocarbon group having 2 to 50 carbon atoms. R ⁷ is an aromatic or aliphatic monovalent to tetravalent organic group having 1 to 30 carbon atoms. a is an integer selected from 1 to 4. (C) hydrosilylation catalyst, (D) storage stability improver. 2. The polymer of component (A) has a molecular weight of 500 to 50,000.
The composition according to claim 1, which is: (3) The substituent (X) in the formula (1) of the component (A) is (R is H, OSi (CH ₃ ) ₃ , or a group selected from organic groups having 1 to 10 carbon atoms, and each R may be the same or different. M is a positive integer, n is 0 or a positive integer,
And 2 ≦ m + n ≦ 50) or (Where R is the same as above, m is a positive integer, n, p, and q are 0
Or a group selected from the group consisting of: a positive integer and 1 ≦ m + n + p + q ≦ 50). 4. The substituent X in the formula (1) of the component (A) is 2. The composition according to claim 1, wherein p is a positive integer, q is 0 or a positive integer, and is a group selected from the group consisting of 2 ≦ p + q ≦ 4. 5. The storage stability improver of component (D) is selected from the group consisting of compounds containing aliphatic unsaturated bonds, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds and organic peroxides. The composition according to claim 1, which is at least one selected from the group consisting of: 6. The storage stability improver of component (D) is dimethyl malate, dimethyl acetylenedicarboxylate,
2. The composition according to claim 1, wherein the composition is at least one selected from the group consisting of 2-pentenenitrile, benzothiazole, 2,3-dichloropropene and quinoline. 7. The composition according to claim 1, wherein the molar ratio of the hydrosilyl group in the component (A) to the alkenyl group in the component (B) is 0.2 to 5.0. 8. The amount of the hydrosilylation catalyst of the component (C) is as follows:
(B) 10 ^-8 to 10 ^-1 based on 1 mol of the alkenyl group in the component.
The composition of claim 1 in the molar range. 9. The amount of the storage stability improver of the component (D) is:
The composition according to claim 1, wherein the amount is in the range of 10 ^-5 to 10 ^-1 mol per mol of the component (A).