JP2978526B2 - 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 containing at least one alkenyl group in the molecule; (B) a non-polymeric organic compound having at least two hydrosilyl groups in the molecule; (C) a hydrosilylation catalyst; and (D) storage stability The present invention relates to a curable composition having excellent storage stability and comprising a stability improver 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 the polyorganohydrogensiloxane and the organic polymer containing an alkenyl group, the polyorganohydrogensiloxane is not separated by phase separation. 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 is fast-curing, and has excellent deep-curing properties, and the cured product has sufficient mechanical properties and excellent storage stability. And a curable composition. That is, when a curing agent composed of an organic compound containing at least two hydrosilyl groups in a molecule is used instead of the polyorganohydrogensiloxane conventionally used in the curing reaction by hydrosilylation, polyorganohydrogen is generally used. It has better compatibility with alkenyl group-containing organic polymers than siloxane. Therefore, if both of the above components are cured using a hydrosilylation catalyst, the components are uniform, have excellent rapid curing and excellent deep curing properties, and the cured product has sufficient mechanical properties such as tensile properties. Since an alkenyl group-containing organic polymer having a high quality can be used, it is possible to provide a cured product which can be applied to a very wide range of uses, and further, a curing having excellent storage stability by blending a storage stability improver. The present inventors have found that a hydrophilic composition can be obtained, and have reached the present invention.

That is, the present invention provides the following components (A), (B) and (C)
And a curable composition having excellent storage stability comprising (D) as an essential component [excluding the case where component (A) is a polyether-based polymer and component (B) is a polyether compound. ].

(A) an organic polymer containing at least one alkenyl group in the molecule; (B) formulas (1) to (4) [X-R ¹ -O _a R ² (1) [X-R ¹ -OC (O) _a R ³ (2) X _a -R ⁴ (3) [X-R ¹ -OC (O) O _a R ⁵ (4) (wherein X is a substituent containing at least one hydrosilyl group. , R ¹ is a hydrocarbon group having 2 to 20 carbon atoms and may contain one or more ether bonds.R ² is an aliphatic 1 to 4 valent organic group having 1 to 30 carbon atoms, R ³ is an aromatic or aliphatic mono- to tetravalent organic group having 1 to 30 carbon atoms, and R ⁴ is a carbon atom having 2 to 2 carbon atoms.
1-4 monovalent hydrocarbon group having 50, R ⁵ is 1 to 4 monovalent organic group of aromatic or aliphatic having 1 to 30 carbon atoms, a is an integer of 1 to 4. (C) a hydrosilylation catalyst, and (D) a storage stability improver, wherein the organic compound contains at least two hydrosilyl groups in the molecule.

As the organic polymer containing at least one alkenyl group in the molecule, which is the component (A) of the present invention, those having various main chain skeletons can be used. First, as a polyether polymer, for example, polyoxyethylene,
Polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer and the like are preferably used. 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, ethylene-propylene-based copolymers, polyisobutylene, Copolymer of isobutylene with isoprene, polychloroprene, polyisoprene, copolymer of isoprene with butadiene, acrylonitrile, styrene, etc., polybutadiene, copolymer of butadiene with styrene, acrylonitrile, etc., polyisoprene, polybutadiene, isoprene Alternatively, a polyolefin-based polymer obtained by hydrogenating a copolymer of butadiene and acrylonitrile, styrene, or the like, a polyacrylic ester, ethyl acrylate, or butyl obtained by radical polymerization of a monomer such as ethyl acrylate or butyl acrylate. Acrylate copolymers such as acrylates such as acrylate and vinyl acetate, acrylonitrile, methyl methacrylate, styrene, etc .; graft polymers obtained by polymerizing vinyl monomers in the organic polymer; polysulfide polymers 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 by condensation polymerization of ε-aminoundecanoic acid Nylon 12 by ring-opening polymerization of ε-aminolaurolactam, polyamide-based polymers such as copolymerized nylon having two or more of the above-mentioned nylons, for example, produced by condensation polymerization from bisphenol A and carbonyl chloride. Polycarbonate-based polymer, Diallyl phthalate polymers, and the like.

The alkenyl group is not particularly limited, but has the formula (5) (Wherein R ⁶ is hydrogen or a methyl group).

About the method of introducing an alkenyl group into the polymer,
Although various proposals can be used, they can be broadly classified into a method of introducing an alkenyl group after polymerization and a method of introducing an alkenyl group during polymerization.

As a method for introducing an alkenyl group after polymerization, for example, an organic group having a functional group such as a hydroxyl group or an alkoxide group at a terminal, main chain or side chain, an active group and an alkenyl group reactive with the above functional group An alkenyl group can be introduced into the terminal, main chain or side chain by reacting an organic compound having Examples of the organic compound having an active group and an alkenyl group having reactivity to the functional group include acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride, acrylic bromide, and the like.
C unsaturated fatty ₃ -C _20, acid halides, acid anhydrides or allyl chloroformate _{(CH 2 = CHCH 2 OCOCl)} , C 3 -C 20 , such as allyl bromo formate (CH ₂ = CHCH ₂ OCOBr) Unsaturated fatty acid-substituted carbonate halide, allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, Butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene and the like.

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

The alkenyl group-containing organic polymer as the component (A) may be linear or branched, and any one having a molecular weight of 500 to 50,000 can be suitably used, but one having a molecular weight of 500 to 20,000 is particularly preferable. The alkenyl group of the component (A) may be present 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.

The non-polymeric organic compound containing at least two bidrosilyl groups in the molecule as the component (B) of the present invention is not particularly limited. However, if a group containing a hydrosilyl group is specifically exemplified, it is represented by- 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) 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 and different. M and n are positive integers And 2 ≦ m + n ≦ 5
0) (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) (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 hydrogensiloxanes represented by, for example, And groups derived therefrom.

Among the above-mentioned various hydrosilyl-containing groups, the molecular weight of the part of the group constituting the hydrosilyl group is small in that the compatibility of the hydrosilyl group-containing organic curing agent of the present invention with various organic polymers is unlikely to be impaired. 500 or less is desirable, further considering the reactivity of the hydrosilyl group,
The following are preferred.

(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 compound (B) may be at least two in one molecule, but is preferably 2 to 15, more 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 hydrosilation catalyst and cured by a hydrosilylation reaction, the number of hydrosilyl groups is preferably 2 or less. 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 hydrosilyl group is represented by the general formula (6) X-R ^1- (6) (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 contain one or more ether bonds.) More specifically, first, the formula (1) (X—R ¹ —O _a R ² (1) (X and R ¹ are the same as above, R ² is an organic group having 1 to 30 carbon atoms, and a is 1
An integer selected from ~ 4. And a compound having an ether bond represented by the formula:

In the formula (1), R ¹ represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and R ¹ may contain one or more ether bonds. Specifically, -CH ₂ CH _2- , -CH ₂ C
H 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 CH ₂ CH _2-
Is preferred.

In the formula (1), R ² is an 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 −, And the like. Of these, the following are preferred.

Next, general formula (2) [X—R ¹ OC (O) _a R ³ (2) (X is a group containing at least one hydrosilyl group, and R ¹ is a divalent hydrocarbon having 2 to 20 carbon atoms. R ³ may be an organic group having 1 to 30 carbon atoms, a may be an integer selected from 1 to 4, and the compound may have an ester bond. Can be

In the formula (2), R ¹ is the same as R ¹ in the formula (1).
R ³ is a C 1-30 aromatic or aliphatic C 1-4
Is a valence organic group. Specifically, CH ₃ −, CH ₃ CH ₂
−, CH ₃ CH ₂ CH ₂ −, − (CH ₂ ) ₅ −, − (CH ₂ ) ₆ −, − (CH ₂ ) ₇ −, And the like. Of these, the following are preferred.

Next, the general formula (3) X _a -R ⁴ (3) (X is a group containing at least one hydrosilyl group, R ⁴ is a monovalent to tetravalent hydrocarbon group having 2 to 50 carbon atoms, and a is 1 And an integer selected from the group consisting of a hydrocarbon having a main chain skeleton represented by the following formula:

In the formula (3), R ⁴ represents a monovalent to tetravalent hydrocarbon group having 2 to 50 carbon atoms. And the like.

Of these,-(CH ₂ ) _n- (n = 2 to 10), Is preferred.

Further, — (CH ₂ ) _n — (n = 2 to 10) is particularly preferred.

(B) Examples of the component, further general formula ^{(4) [X-R 1} -OC (O) O a R 5 (4) (X is a group containing at least one hydrosilyl group, R ¹ is carbon A divalent hydrocarbon group having 2 to 20 carbon atoms, which may contain one or more ether bonds, and R ⁵ 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.) and has a carbonate bond.

Wherein, R ¹ has the formula (1), which is the same as R ¹ in (2). As R ⁵ is, (N is an integer of 2 to 10) And the like. Of these, the following are particularly preferred.

The hydrosilyl group-containing organic compound as the component (B) has a molar ratio of the hydrosilyl group to the alkenyl group as the component (A).
It is preferable to use in the range of 0.2 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.

The method for producing the hydrosilyl group-containing organic compound as the component (B) is not particularly limited, and any method may be used. For example, (i) an organic compound having a Si—Cl group in a molecule is treated with a reducing agent such as LiAlH ₄ , NaBH _{4, and the} like.
A method of reducing a —Cl group to a Si—H group, (ii) reacting an organic compound having a functional group X in a molecule with a compound having a functional group Y and a hydrosilyl group simultaneously reacting with the above functional group in the molecule. (Iii) a method of selectively hydrosilylating a polyhydrosilane compound having at least two hydrosilyl groups with respect to an organic compound containing an alkenyl group so that the hydrosilyl groups remain in the molecule of the compound even after the reaction. And so on. Of these (ii
The method i) is particularly preferred.

Examples of the hydrosilylation catalyst as the component (C) of the present invention include platinum alone, solid platinum supported on a carrier such as alumina, silica and carbon black, platinum chloride, 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 (A). 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. Also, the hydrosilylation catalyst is generally expensive and corrosive, and it is preferable not to use the hydrosilylation catalyst in an amount of more than 10 ^-1 mol because a large amount of hydrogen gas is generated and a cured product may foam.

When the hydrosilyl group-containing organic compound as the component (B) of the present invention is produced by the above-mentioned selective hydrosilylation,
Even after the reaction, since the component (B) 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 groups are converted to Si—OH groups. 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 (B). 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 ¹⁴ and R ¹⁵ are a hydrogen atom, an alkyl group, an aryl group, or R ¹⁴ and R ¹⁵ are connected to each other at the other end) represented by the general formula (8) Wherein R ¹⁶ , R ¹⁷ and R ¹⁸ are hydrogen atoms or hydrocarbon groups, and the total number of carbon atoms of R ¹⁶ , R ¹⁷ and R ¹⁸ is 2-6. When R ¹⁶ , R ¹⁷ and R ¹⁸ are hydrocarbon groups, R ¹⁶ and R ¹⁷ or R ¹⁷ and R ¹⁸ may be mutually connected at the other end. ) (Wherein R ¹⁹ , R ²⁰ and R ²¹ are a hydrocarbon group having 1 to 10 carbon atoms, provided that R ²⁰ and R ²¹ may be mutually connected at the other end. ), General formula (10) (Wherein at least one of R ²² is a hydrocarbon group having an acetylenic unsaturated bond) represented by general formula (11) Wherein R ^{23 to} R ²⁷ are a hydrogen atom, a halogen or a monovalent hydrocarbon group, X is a halogen or an alkoxy group such as chlorine or bromine, a tetramethylvinylsiloxane cyclic substance, 2-pentene Nitrile, general formula (12) (Wherein R ²⁸ is a monovalent organic group containing at least one acetylene bond), an aliphatic carboxylic acid ester of an olefinic alcohol such as vinyl acetate,
Alkyl acetylenedicarboxylate represented by the general formula (13) R ²⁹ O ₂ CC CC—CO ₂ R ²⁹ (13) (where R ²⁹ is a hydrocarbon group such as methyl and ethyl); 1
Four) (In the formula, R ³⁰ 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, the general formula _{^{(15) R 31 2 NR 33}} NR 32 2 (15) a diamine compound represented by (wherein the alkyl group R ³¹ is containing from 1 to 4 carbon atoms, R ³² is hydrogen Or R ³¹ and R
³³ 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 since the viscosity increase of the component (B) is almost completely suppressed even at a relatively high temperature (about 50 ° C.).

The amount of the component (D) can be selected almost arbitrarily 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 per mol. This is because if the amount is less than 10 ^-6 mol, the storage stability of the component (B) 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 storage form of the composition of the present invention is not limited except that the component (D) is contained in the component (B). For example, since the component (D) not only improves the storage stability of the component (B) but also has the function of delaying the curing by the addition reaction of the components (A) and (B), the composition of the present invention is 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 (C) and the component (B) and the component (D) each constitute one package. If one package is used, it is preferable to store at a low temperature (0 ° C. or lower).

(B) and (C) containing the components (A) and (D) of the present invention.
If the components are mixed and cured, a uniform cured product having excellent deep curability can be obtained. The curing conditions are not particularly limited, but are generally 20 to 200 ° C, preferably 50 to 150 ° C for 10 seconds to 4 hours.
It is good to cure for a time. Especially at high temperatures of 80-150 ° C
A product which cures in a short time of about 1 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. Further, the components (A) to (D) are kept at a low temperature (−60).
-5 ° C.) and curing at a relatively low temperature (25-100 ° C.) can also suppress foaming. The properties of the cured product depend on the main chain skeleton, molecular weight, etc. of the polymers of the components (A) and (B), but can be prepared from rubber to resin.

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, 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 2 300 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 3 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 ¹ H 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 data) Hydroxyl content (meq / g) 0.90 Viscosity (poise / 30 ℃) 70 Average molecular weight [VPO measurement] 2500 Synthesis Example 4 Stirrer bar, dropping funnel, thermometer 3, One four-necked flask equipped with a side cock and a condenser 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 substantially transparent solution was obtained by suction filtration using a filter aid (diatomaceous earth). This solution was evaporated, and further dried under reduced pressure at 80 ° C. for 3 hours to obtain about 26 g of a pale yellow viscous liquid oligomer. 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 5 A 200 ml four-necked flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a cooling tube was prepared. Next, under a nitrogen atmosphere, cyclic hydrogen polysiloxane 29.73 g (124 mmol) (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged into the flask. Isophthalic acid diallyl (manufactured by Wako Pure Chemical Industries, Ltd.) ester 9.84 g (40 mmol) and chloroplatinic acid catalyst solvent solution _{H 2 PtCl 6 · 6H 2 O} 1.0g ethanol / 1,2
-82 μm dissolved in 9 g of dimethoxyethane (1/9 V / V)
Was dissolved in 100 ml of toluene, mixed well, and then charged into a dropping funnel. The flask was heated to 65-70 ° C and the toluene solution was added dropwise over 100 minutes. At the time when the reaction was further performed for 1 hour, an IR spectrum was taken. Since the absorption derived from the olefin at 1640 cm ^-1 had completely disappeared, the reaction was completed at this time. After removing volatile matter from the reaction mixture by evaporation, the residue was dried under reduced pressure at 80 ° C. for 1 hour to obtain 25.85 g of a pale yellow viscous liquid.
The viscous liquid was identified by 300 MHz ¹ H NMR, IR spectrum and the like to have 86% of an Si-H-containing ester compound [n = 1 (MW = 1214) having the following structural formula, and (n = 2 (MW = 1701) )
Is a mixture consisting of 14%).

Synthesis Example 6 A 200 ml four-necked flask was equipped with a cooling tube with a three-way cock.
A device equipped with an equalizing dropping funnel, a thermometer, a magnetic chip, and a glass stopper was prepared. Cyclic polyhydrogensiloxane under N ₂ 12.03 g (50 mmol) (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) and 20 ml of toluene were charged in a flask. 1,9-decadiene
2.76 g (20 mmol), chloroplatinic acid catalyst solution _{(H 2 PtCl 6 · 6H 2} O
A solution in which 1 g was dissolved in ethanol 1 g and 1,2-dimethoxyethane 9 g) 20 μl in toluene 30 ml was charged into a dropping funnel. The flask was placed in a 50 ° C. oil bath, and the toluene solution was dropped into the flask over 2 hours under a N ₂ atmosphere. At the time when the reaction was further performed at 50 ° C. for 1 hour after the completion of the dropping, the IR spectrum was measured to be 1640 cm
^The reaction was terminated at this point because the absorption of olefin near ^-1 had completely disappeared. The toluene solution after the completion of the reaction was washed with a saturated aqueous solution of ammonium chloride (100 ml × 2) and exchanged water (100 ml × 1), and dried over NaSO ₄ . Na ₂ SO ₄
Was removed by filtration, volatile matter was removed by evaporation, and then degassed under reduced pressure at 80 ° C. to obtain 9.11 g of a colorless and transparent liquid. The hydrosilyl group in the hydrocarbon compound is 21
It was confirmed as a strong absorption of 70 cm ^-1 . 300MHz NMR
In Si- intensity ratio of protons between the peak and the Si-C H ₃ of H the compounds by comparing the intensity ratio of the (measured value 0.216) and the calculation has the structure of formula average [n = 1
(MW = 998) was 53%, and n = 2 (MW = 1377) was 47%]. Based on this, Si in unit weight
The calculated number of —H groups was 0.769 mol / 100 g.

Synthesis Example 7 A 200 ml four-necked flask was equipped with a cooling tube with a three-way cock.
A device equipped with an equalizing dropping funnel, a thermometer, a magnetic chip, and a glass stopper was prepared. Cyclic polyhydrogensiloxane under N ₂ 12.03 g (50 mmol) (LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.) and 20 ml of toluene were charged in a flask. Diethylene glycol diallyl carbonate (RAV-7N, manufactured by Mitsui Petrochemical Co., Ltd.) 5.49 g (20 mmol),
Chloroplatinic acid catalyst solution chloride _{(H 2 PtCl 6 · 6H 2} O 1g ethanol 1
g, a solution dissolved in 9 g of 1,2-dimethoxyethane) (41 μl) in 50 ml of toluene was charged into a dropping funnel. The flask was placed in a 50 ° C. oil bath, and the toluene solution was dropped into the flask over 1.5 hours under a N ₂ atmosphere. When the IR spectrum was measured after the completion of the dropping, 1640 cm
^The reaction was terminated at this point because the absorption of olefin near ^-1 had completely disappeared. The reaction mixture was evaporated to remove volatiles to obtain 10.2 g of a slightly viscous pale yellow light liquid. The hydrosilyl group of the carbonate compound was confirmed as a strong absorption at 2170 cm ^{-1 in} the IR spectrum. The peak of the Si- H in NMR of 300MHz and Si-C _{H 3}
By comparing the calculated intensity ratio with the proton intensity ratio (actually measured value 0.181), it was found that the compound had a structure of the following formula on average. Based on this, the number of Si-H groups in the unit weight was calculated to be 0.47 mol / 100 g.

A: Storage stability test (1) To the hydrocarbon-containing Si-H group-containing compound produced in Synthesis Example 6, 30 equivalents of various storage stability improvers were added to platinum, and each was stored at 50 ° C. The change with time of the Si-H value (the number of moles of Si-H groups contained per unit weight of the compound) was measured. The results are shown in Table 1.

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

B: Compatibility test In order to examine the compatibility between the allyl group-containing organic polymer produced in Synthesis Examples 1, 2, 3, and 4, and the Si—H group-containing organic compound produced in Synthesis Examples 5, 6, and 7, A predetermined amount of both components was mixed in a combination as shown in Table 2, and after centrifugal defoaming, the mixed state was observed.

The allyl group-containing organic polymer of Synthesis Example 1 is any Si-H
It was well compatible with the group-containing compound. The compatibility was generally good for the other combinations.

C: Curability test Compatibility was good in the compatibility test of B above (A)
(B) For the combination of both components, a chloroplatinic acid catalyst solution [component (C)] was added and thoroughly mixed in order to examine the curability. As the storage stability improver [component (D)], those shown in Table 3 were used. A part of the mixture was taken on a gel tester (manufactured by Nissin Kagaku Co., Ltd.), and the snap-up time (time until rubber elasticity) was measured at 80 ° C. The results are shown in Table 3, and it was found that the composition was quick-curing at high temperatures.

D: Deep Curability Test The composition used in the above (C) was examined for its deep curability. That is, these mixtures were poured into a polyethylene container having a height of 10 cm and an inner diameter of 1 cm to a position of 5 cm in height, centrifuged and defoamed, and then cured at 100 ° C. for 1 hour. When a 1 cm portion was cut out from the lower part of the container and the curability was examined, a uniform cured product was obtained in any combination. From this result, it was found that the composition of the present invention was excellent in deep-section curability.

E: Dumbbell physical properties of cured product Alkenyl group-containing organic polymer [component (A)], Si-H
A predetermined amount of the group-containing compound [component (B)] and the chloroplatinic acid catalyst solution [component (C)] were stirred and mixed. As the storage stability improver (component (D)), those shown in Table 4 were used. The mixture was defoamed by centrifugation and poured into a polyethylene mold. After defoaming again at room temperature under reduced pressure, the mixture was cured at 100 ° C. for 1 hour to obtain a uniform rubbery cured product having a thickness of 3 mm. A No. 3 dumbbell compliant with JIS K 6301 was punched out of 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 4.

[Effects of the Invention] According to the present invention, a cured product which is excellent in fast-curing property, deep-curing property, mechanical properties and storage stability is provided.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuya Yonezawa 5-12-11 Tsutsujigaoka, Tarumizu-ku, Kobe City, Hyogo Prefecture (56) References JP-A-1-138230 (JP, A) JP-A-56-20051 (JP) JP-A-61-141758 (JP, A) JP-A-62-294239 (JP, A) JP-A-52-132064 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB Name) C08L 1/00-101/14

Claims (13)

(57) [Claims] 1. A curable composition having excellent storage stability comprising the following components (A), (B), (C) and (D) as essential components, provided that the component (A) is a polyether-based polymer. Except when they are coalesced and the component (B) is a polyether compound. (A) an organic polymer containing at least one alkenyl group in the molecule, (B) formulas (1) to (4) [X-R ¹ -O _a R ² (1) [X-R ^{1 _{-OC (O) a R 3 (}} 2) X a -R 4 (3) ^{[X-R 1 -OC (O)} O a R 5 (4) ( wherein, X comprises at least one hydrosilyl group The substituent R ¹ is a hydrocarbon group having 2 to 20 carbon atoms and may have one or more ether bonds, and R ² is an aliphatic monovalent to tetravalent organic group having 1 to 30 carbon atoms. Group, R ³ is an aromatic or aliphatic mono- to tetravalent organic group having 1 to 30 carbon atoms, and R ⁴ is a carbon atom having 2 to 2 carbon atoms.
1-4 monovalent hydrocarbon group having 50, R ⁵ is 1 to 4 monovalent organic group of aromatic or aliphatic having 1 to 30 carbon atoms, a is an integer of 1 to 4. (C) a hydrosilylation catalyst, and (D) a storage stability improver, wherein the organic compound contains at least two hydrosilyl groups in the molecule. 2. The organic polymer of the component (A) is represented by the formula (5): (Wherein R ⁶ is hydrogen or a methyl group) The curable composition according to claim 1, which is a compound having at least one alkenyl group represented by the following formula: 3. A compound of the formula (1) wherein R ² is —CH ₂ CH ₂ — and —CH
₂ CH (CH ₃₎ - curable composition of claim 1 wherein is selected from the group consisting of. 4. A method according to claim 1, wherein R ³ in the formula (2) is-(CH ₂ ) ₂ -,-
_{(CH 2) 3 -, -} (CH 2) 6 -, ortho -C ₆ H ₄ -, meta -
C ₆ H ₄ - and para -C ₆ H ₄ - curable composition of claim 1 wherein is selected from the group consisting of. 5. The method according to claim 3, wherein R ^{4 in the} formula (3) is-(CH ₂ ) _n-
(N is an integer of 2 to 10) and The curable composition according to claim 1, which is selected from the group consisting of: 6. A compound of the formula (4) wherein R ⁵ is —CH ₂ CH ₂ OCH ₂ CH ₂
-, -CH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ -and -CH ₂ CH (CH ₃ ) OCH ₂
CH (CH ₃₎ - curable composition of claim 1 wherein is selected from the group consisting of. 7. The method according to claim 1, wherein the substituent X containing at least one hydrosilyl group is of 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 is a positive integer, n is 0 Or a positive integer and 2 ≦ m + n ≦ 50) (Where R is the same as above, m is a positive integer, n, p, and q are 0
Or a group represented by a positive integer and 1 ≦ m + n + p + q ≦ 50). 8. A method according to claim 1, wherein the substituent X containing at least one hydrosilyl group has the formula The curable 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. 9. The storage stability improver of component (D) is selected from the group consisting of compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds and organic peroxides. The curable composition according to claim 1, which is at least one selected from the group consisting of: 10. The storage stability improver of component (D) is dimethyl malate, dimethyl acetylenedicarboxylate, 2-pentenenitrile, benzothiazole, 2, 3,
The curable composition according to claim 1, which is at least one member selected from the group consisting of -dichloropropene and quinoline. 11. The curable composition according to claim 1, wherein the molar ratio of the alkenyl group in the component (A) to the hydrosilyl group in the component (B) is 0.2 to 5.0. 12. The amount of the hydrosilylation catalyst of the component (C) is from 10 ^-6 to 1 mol of the alkenyl group in the component (A).
A curable composition according to claim 1 in the range of 10 ^-3 mole. 13. The amount of component (D), a storage stability improver,
The curable composition according to claim 1, wherein the amount is in the range of 10 ^-5 to 10 ^-1 mol per 1 mol of the component (B).