JPH03188166A - Curable composition of excellent storage stability - Google Patents

Abstract

PURPOSE:To obtain a curable composition which excels in rapid curability and deep curability, can give a cured product of high mechanical properties and excels in storage stability by mixing an alkenylated polymer with a polymer containing at least two hydrosilyl groups, a hydrosilylation catalyst and a storage stability improver. CONSTITUTION:A storage-stable curable composition is formed from a polymer having a mol.wt. of 500-50000 and containing at least one alkenyl group of formula I [wherein R<1> is -R<2>-, -R<3>-O-R<4>-, -R<3>-OCO- or -R<3>CO- (wherein R<2>, R<3> and R<4> are each a 1-20C bivalent hydrocarbon group); R<5> is H or CH3; and n is 0 or 1], a polymer having at least two hydrosilyl groups in the molecule and represented by formula II (wherein X is a hydrosilyl group of formula III (wherein R is H, OSi(CH3)3, a 1-10C organic group or the like), a hydrosilylation catalyst (e.g. Pt catalyst), and a storage stability improver (e.g. a compound having an aliphatic unsaturated bond or an organophosphorous compound) as the essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a curable composition, and more particularly to (A) an organic polymer containing at least one alkenyl group in the molecule; The present invention relates to a curable composition with excellent storage stability, which contains as essential components an organic polymer having at least two hydrosilyl groups, (C) a hydrosilylation catalyst, and (D) a storage stability improver.

[Conventional technology and problems]

Conventionally, various 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 a polyorganohydrodiene siloxane having two or more has been developed,
Utilizing its excellent weather resistance, water resistance, and heat resistance, it is used as a sealant and botting 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 when attempting to cure polyorganovinylsiloxanes and organic polymers containing hydrosilyl groups, phase separation occurs in organic polymers containing hydrosilyl groups. There was a problem in that the hydrolysis and dehydrogenation condensation reactions of the coalescence were promoted, and sufficient mechanical properties could not be obtained due to voids.

[Means for solving problems]

In view of the above circumstances, as a result of intensive research, the present invention has solved these problems and is fast-curing, has excellent deep-curing properties, provides a cured product with sufficient mechanical properties, and has excellent storage stability. The present invention provides a curable composition. That is, if an organic polymer containing at least one alkenyl group in the molecule is used instead of the polyorganovinylsiloxane conventionally used in the curing reaction by hydrosilylation, the hydrosilyl Good compatibility with organic polymers containing groups. Therefore, if both of the above components are cured using a hydrosilylation catalyst, it will be uniform, fast curing, and has excellent deep curing properties, and the cured product will have sufficient mechanical properties such as tensile properties.
The present inventors have discovered that a curable composition with excellent storage stability can be obtained by further incorporating a storage stability improver.

That is, the present invention provides a curable composition with excellent storage stability comprising the following components (A), (B), (C), and (D) as essential components; (A,) at least one in the molecule; (B) an organic polymer containing at least two hydrosilyl groups in the molecule; (C) a hydrosilylation catalyst; (D) a storage stability improver.

The content is as follows.

As the organic polymer containing at least one alkenyl group in the molecule, which is component (A) of the present invention, 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, copolymers of isoprene or butadiene, acrylonitrile, styrene, etc. Polyolefin polymers obtained by adding polyacrylic esters obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate, acrylic esters such as ethyl acrylate and butyl acrylate, and vinyl acetate, acrylonitrile, methyl methacrylate, and styrene. etc., graft polymers obtained by polymerizing vinyl chloride in the above-mentioned organic polymers, polysulfide polymers, nylon 6 obtained by ring-opening polymerization of ε-aminocaprolactam, hexamethylene. Nylon 66 produced by polycondensation of diamine and adipic acid, nylon 610 produced by polycondensation of hexamethylene diamine and sebacic acid, and nylon 11 produced by polycondensation of ε-aminoundecanoic acid. Nylon 12 produced by ring-opening polymerization of ε-aminolaurolactam, polyamide-based polymers such as copolymerized nylon containing two or more of the above-mentioned nylons, for example, polyamides produced by condensation polymerization of bisphenol A and carbonyl chloride. Examples include carbonate polymers and diallyl phthalate polymers.

The alkenyl group is not particularly limited, but is represented by formula (I) % formula % (I) [R+ is represented by formula 0 (wherein R2, R3, and R4 are divalent hydrocarbon groups having 1 to 20 carbon atoms) A group selected from divalent organic groups, R
5 is hydrogen or a methyl group, and a is an integer of 0 or 1. ] Preferred are alkenyl groups represented by the following.

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

As a method for introducing an alkenyl group during polymerization, for example, an active group and an alkenyl group that are reactive toward the above 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 group. 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.
,-C,. unsaturated fatty acids, acid halides, acid anhydrides, etc. and allyl chloroformate (CH□=CHCH!0COC
I), allyl bromoformate CCH1=CHCHg
Cs Cz such as 0COBr). 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, 1
-hexenyl(chloromethoxy)benzene, allyloxy(chloromethyl)benzene, and the like.

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, vinyl 7, which has an alkenyl group with low radical reactivity in the molecule, such as allyl methacrylate and allyl acrylate, can be used. By using a radical chain transfer agent having an alkenyl group with low radical reactivity such as mercaptan or allyl mercaptan, an alkenyl group can be introduced into the main chain or terminal of the polymer.

The alkenyl group-containing organic polymer as component (A) may be linear or branched, and has a molecular weight of 500 to 5000.
0 can be suitably used, but 500 to 200
00 is particularly preferred.

The alkenyl group of component (A) may be located at the end of the molecule or in the molecule, but when producing a rubber-like cured product using the composition of the present invention, it is better to have it at the end of the molecule to form a more effective network. This is preferable because the chain length becomes longer.

There are no particular limitations on the method for producing the organic polymer containing at least two hydrosilyl groups in the molecule, which is component (B) of the present invention, but for example, at least one alkenyl group in one molecule of component (A). It can be produced by reacting an organic polymer containing a group with a polyvalent hydrogen silicone compound (component (E)) in the presence of a hydrosilylation catalyst so that the hydrosilyl group remains after the reaction.

In this case, polyvalent hydrogen silicon compounds that can be used as component (E) include (C1ls> x
sitlg, (cJs) zsiH□+ CH35i
Hs, CJsSiH3, (Czlls) zSiHt
, CHs (CHz) Monosilane compound represented by 5siHs; H(CH35iHs(CHs)J+ H(
CH3)xsicHlcHtsi (CHs) zHl H(C)Iz)tsisi(CHs)I(x, H<
CHshSiNH5+ (CHsun1 H+111(C)
I*)xs+]J, H(CHrizsiOc(CH3)
・Polysilicon compounds such as N5i(CHs)χH; (CHs)ssi 0−←5i−0÷r−(S i −0←TH5+ O
Juice, 5i (CHs) x CHs CJs
CHsHs CH.

CHs CH3 H(II=2~50) (CHs)ssi O−←Si O±, 5i(
CHs)3zHs CJ5CJ Si-+-0 CH.

Si　H)s CH.

CHs CH3 L CH3 CHz CHCb Hs H3 C-〇l? (b+c=3-6, b≧2), R5i [0Si(CHi)J) 5 (R=CHff.

C4H6゜ organic groups such as CJs) R,5iO5iO5iO3jRs (R=C11,.

C,)Is.

Ct H.

Organic groups such as H
The following are preferable, and furthermore, in terms of high reactivity during the hydrosilylation reaction between component (A) and component (E) described later, C)13 (CHs)ssiO+5i-0+-05i(CHz)s
H(II・3-5) n CH, C, H, CH3H-5i -0
-5t-H (CH3>TSi0 0Si (CH3) s
Examples include various chain, branched, and cyclic polyvalent hydrogen polysiloxanes shown in the following. The number of hydrosilyl groups in one molecule of the polyvalent hydrogen silicone compound of component (E) is preferably 2 to 15, particularly 3 to 15.
12 is preferable, and it is preferable that the hydrosilyl group-containing organic polymer of component (B) produced from components (A) and (E) is I C11s ■ HCHs.Furthermore, unreacted components are removed after the hydrosilylation reaction. ■CH in that it is easy to remove under reduced pressure.

CI(.

is particularly preferred.

The hydrosilyl group-containing organic polymer, which is the component (B) of the present invention, is produced by a hydrosilylation reaction between the alkenyl group-containing organic polymer, which is the component (A), and the polyvalent hydrogen silicone compound, which is the component (E). Catalysts used for production include simple platinum, solid platinum supported on a carrier such as alumina, silica, and carbon black, chloroplatinic acid, and chloroplatinic acid with alcohol, aldehyde, ketone, etc. complex, platinum-olefin complex (e.g., Pt(C)Iz=CHa)g(pphs)□PtC
CHz=C1h)zcI2); platinum-vinylsiloxane complex (e.g. pt(ViMelSiO3iMe=V
i), , Pt ((MeViSiO)4) @);
Platinum-phosphine complexes (e.g., Pt(PPt+s)4
, Pt(PBuz) a ); platinum-phosphite complex (e.g., Pt (P(OPhs) a , Pt
(P(OBu)z)a) (wherein, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, ph is a phenyl group, and n and m are integers), dicarbonyldichloroplatinum, or , As-hby, U.S. Pat. Nos. 3,159,601 and 3,159,662, and Lamoreau (L.
Also mentioned are the platinum alcoholade catalysts described in U.S. Pat. No. 3,220,972 by A.

Additionally, Modi-C U.S. Patent No. 3516
The platinum chloride-olefin complexes described in '946 are also useful in the present invention.

In addition, examples of catalysts other than platinum compounds include RhCI (
PPhz)s, RhC11,Rh+AIgO1,Ru
C1z, IrCl3+ FeCl, AlCl2.
PdC1z・2H! 01 N+CIt+ T+CIa
etc. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, etc. are preferred. The amount of catalyst is particularly Although there is no restriction, it is preferable to use it in a range of 1 O-' to 10-' mol per 1 mol of alkenyl group in component (A).
It is preferably used in a range of 10-3 to 10-'mol.

The use of a solvent is not particularly required in the hydrosilylation reaction, but if the starting material has a high viscosity and operations such as stirring are difficult, an inert organic solvent may be used as appropriate. These include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as hexane and octane, ether solvents such as ethyl ether and butyl ether, ketone solvents such as methyl ethyl ketone, and halogen solvents such as trichloroethylene. Examples include hydrogenated hydrocarbon solvents.

Regarding the method of adding both components (A) and (E) and the hydrosilylation catalyst, there is a method of adding the three components at once, a method of adding the component (A) and the hydrosilylation catalyst to the component (E), a method of adding the component (A) and the hydrosilylation catalyst to the component (E), Possible methods include adding component A) to component (E) and the catalyst, adding component (E) to component (A) and the hydrosilylation catalyst, and adding each component simultaneously. There is no particular restriction, but in order to react so that the hydrosilyl group remains after the reaction, we believe that it is desirable that the polyvalent hydrogen silicon compound, which is the component (E), always be present in excess of the component (A). Therefore, it is preferable to add a mixture of an alkenyl group-containing organic polymer (A) and a hydrosilylation catalyst to a polyvalent hydrogen silicon compound (E) at a reaction temperature of 0. is 0 to 200°C, preferably 50 to 150°C. If the reaction temperature is lower than 0°C, the catalyst activity will be insufficient and the reaction rate will be slow.

Moreover, when the temperature rises above 150°C, the catalyst is often deactivated.

When component (A) and component (B) used in the present invention have the same main chain skeleton, the two components have good compatibility. On the other hand (A)
If the main chain skeletons of component and (B) are different, (A),
CB) Compared to a combination in which one of the two components is replaced with a polysiloxane polymer, the compatibility of these two components is improved, as estimated from the SP value (solubility parameter), but it is not completely uniform. This is not always the case, and it may become cloudy. However, for example, polycaprolactone, hydrogenated polyisobrene and n-butyl acrylate
In combinations of acrylic ester polymers containing more than % by weight and hydrogenated polyisobrene, (A) and (B
) shows good compatibility even if the main chain skeletons of the components are different.

As the hydrosilylation catalyst which is the component (C) of the present invention, the hydrosilylation catalyst used in the production of the hydrosilyl group-containing organic polymer which is the component (B) from the component (A) and the component (E) described above is used. Catalysts can be suitably used. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, etc. are preferred.

There is no particular restriction on the amount of the catalyst, but it is preferably used in the range of 10-' to 10-@mol, preferably 10-3 to 10-' per mol of alkenyl group in component (A).
It is preferable to use it in the mol range *10-'a+.

If it is less than 1, curing will not proceed sufficiently, and hydrosilylation catalysts are generally expensive and ah-prone, and a large amount of hydrogen gas may be generated and the cured product may foam, so it is recommended to use IQ-'mo1 or more. It's better not to be there.

Since the hydrosilyl group-containing organic polymer, which is the component (B) of the present invention, usually contains a hydrosilylation catalyst, its stability is generally poor, and if it is left for a long time or is contaminated with moisture, the 5i-H group Conversion to 5iOH groups occurs, and phenomena such as increased viscosity and gelation are observed. Therefore, it is essential to include a storage stability improver as component (D) in component (B). Furthermore, although component (D) deactivates the hydrosilylation catalyst at low temperatures, it no longer inhibits the hydrosilylation reaction at relatively high temperatures, so the composition of the present invention provides a cured product with excellent mechanical properties.

As component (D), compounds containing aliphatic unsaturated bonds, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin-based compounds, organic peroxides, etc. can be used favorably.

Compounds containing an aliphatic unsaturated bond include the general formula (I[
l) Propargyl alcohol represented by 6 H-C-=C-C-OH (III) (wherein R&, Rt are hydrogen atoms, alkyl groups, aryl groups, or 16° are interconnected at the other end) ), an en-yne compound represented by the general formula () % formula % (wherein R", R1, R
10 is a hydrogen atom or a hydrocarbon group, Rg, Rq,
The total number of carbon atoms in RIO is 2-6. However, R6
゜When R9, Rlo is a hydrocarbon group, R11, R
9 or R'', R'° may be mutually connected at the other end), a silane compound represented by the general formula (V) RIt R''Si-←OCC:CI)s (V)I2 (In the formula, R++, RIt,
R13 is a hydrocarbon group having 1 to 10 carbon atoms, provided that RIz
and R13 may be mutually connected at the other end. ), a polysiloxane compound represented by the general formula (Vl) R14RI4 (in the formula, at least one of R+4 is a hydrocarbon group having an acetylenically unsaturated bond), an olefinic compound represented by the general formula (■) RIt ( In the formula, RIS, R19
is a hydrogen atom, halogen or monovalent hydrocarbon group, X is chlorine,
halogens such as bromine or alkoxy groups), tetramethylvinylsiloxane cyclic bodies, 2-pentenenitrile, compounds represented by the general formula (■) (wherein Hzo is a monovalent organic group containing at least one acetylene bond) ), aliphatic carboxylic acid ester of olefinic alcohol such as vinyl acetate, general formula (IX) R"ChC-C:: C-C0□R" (IX
) Alkyl acetylene dicarboxylate (
During the ceremony, 17! + is a hydrocarbon group such as methyl, ethyl, etc.), a maleic acid ester represented by the general formula (X) (hydrocarbon group), diorganofumarate, etc.

Examples of organic phosphorus compounds include triorganophosphine, diorganophosphine, triorganophosphite,
Examples include organophosphonic acids.

Examples of organic sulfur compounds include organomercaptan, diorganosulfide, diorganosulfoxide, mercapto group-containing organosilanes, hydrogen sulfide, benzothiazole, penzothiazole disulfite, 2-(4-morphosynyldithio)benzothiazole etc. are exemplified.

Examples of nitrogen-containing compounds include ammonia, primary to tertiary alkylamine, arylamine, alkylarylamine,
N,N-diorgano-amino alcohol, urea, thiourea, pyrimidine, pico I77, hydrazine, sulfonic acid amide, benzotriazole, quinoline, triallylisocyanurate, general formula (XI) R1″JR”NR” (X I ) Examples include diamine compounds represented by (wherein R13 is an alkyl group containing 1 to 4 carbon atoms, R14 is hydrogen or Ro, and RlS is an alkyl group containing 2 to 4 carbon atoms). .

Examples of tin-based compounds include stannous halides dihydrates and stannous carboxylates.

In addition, the peroxides used in the punching machine include di-mono-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy), and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane.
-butylperoxy) 3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as α,+-bis(t-butylperoxy)isopropylbenzene, benzoyl peroxide,
diacyl peroxides such as p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, peracid esters such as t-butyl perbenzoate,
Peroxydicarbonates such as diisopropyl perdicarbonate, di-2-ethylhexyl perdicarbonate, 1,1-di(
L-butylperoxy)cyclohexane, 1,1-di(L
-Butylperoxy)-3,3,5-trimethylcyclohexane and other peroxyketals are exemplified.

Among these, component (B) suppresses the increase in viscosity at room temperature for a long period of time and is easy to handle.
dialkyl maleate, dialkyl acetylene dicarboxylate, 2-pentenenitrile, benzothiazole,
Quinoline, 2.3 dichloropropene are preferred, furthermore,
Particularly preferred are 2-pentenenitrile, benzothiazole, and quinoline, since they almost completely suppress the increase in viscosity of component (B) even at relatively high temperatures (about 50°C).

The amount of component (D) to be used can be almost arbitrarily selected as long as it is uniformly dispersed in the organic polymers of components (A) and (B), but it is per mole of the hydrosilylation catalyst of component (C). The storage stability improver component (D), which is preferably used in an amount of 2 to 10,000 moles, may be used alone or in combination of two or more.

There is no restriction on the storage form of the composition of the present invention, except that the component (D) is contained in the component (B). For example, the storage stability of the component (D) is The composition of the present invention can be packaged in one package because it not only improves the properties of the composition but also retards the curing caused by the addition reaction between components (A) and (B). However, from the viewpoint of long-term storage stability, it is preferable to use a two-pack type composition, for example, containing components (A) and (C) and components (B) and (D) in one package. If it is packaged in one package, it is preferable to store it at low temperature (below 0°C).

By mixing and curing components (B) and (C) including components (A) and (D) of the present invention, a uniform cured product with excellent deep curability can be obtained. There are no particular restrictions on curing conditions, but generally 20 to 200°C, preferably 50 to 150°C.
It is best to cure for 10 seconds to 4 hours, especially 80 to 150
At high temperatures at C, some products can be cured in a short time of about 10 seconds to 1 hour.0 Foaming phenomenon may be observed at the stage of curing the composition, but if the composition contains iron, cobalt, nickel, copper, By adding transition metal powder such as , tungsten, etc., foaming can be suppressed.
Foaming can also be suppressed by mixing component D) at a low temperature (-60 to 5°C) and curing it at a relatively low temperature (25 to 100°C). The properties of the cured product are used (A)
Depending on the main chain skeleton, molecular weight, etc. of the polymer of component (B), it is possible to produce anything from a rubber-like material to a resin-like material.

When producing a cured product, in addition to the four essential components (A), (B), (C), and (D), depending on the purpose of use, a solvent, an adhesion improver, a physical property regulator, and a preservative are added. Stability improver, plasticizer, filler, anti-aging agent, ultraviolet absorber, metal deactivator, ozone deterioration inhibitor, light stabilizer, amine radical chain inhibitor, phosphorus peroxide decomposer, lubricant , pigments, foaming agents, and other various additives may be added as appropriate.

The cured product of the present invention can be applied to various uses.

Examples include adhesives/adhesives, paints, waterproofing agents for coatings, foam sealants, botting agents for electrical and electronic applications, films, cosmetics, medical molded products, dental impression agents, etc.

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

Polyoxypropylene glycol with an average molecular weight of 3.3000 and powdered caustic soda were stirred at 60"C, bromochloromethane was added to carry out the reaction, and the molecular weight was increased. Next, allyl chloride was added and the mixture was heated to 110"C. The terminals were allyl etherified.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 2 1j equipped with a stirring bar, dropping funnel, thermometer, 3-way pot, and cooling tube! Four Lough flasks were prepared.

Next, in a nitrogen atmosphere, 41.7 g (0,173 sol) of cyclic polysiloxane (manufactured by Shin-Etsu Chemical, LS8600)
) was charged into a flask. 300 g of the polypropylene oxide synthesized in Synthesis Example 1 in which 92% of the molecular ends are allyl groups (number of moles of allyl groups: 0.069 sol), 230 x l of toluene, and chloroplatinic acid M solvent (Hffi).
PtCI6・6Hz01g in ethanol III, 1
．． Solution dissolved in 2-dimethoxyethane 9Id) 83
A toluene solution consisting of .mu.l was charged into the dropping funnel. The flask was heated to 70"C, and the toluene solution was added dropwise at a rate of about 21d per minute over 5 hours.The reaction temperature was then raised to 80°C and after stirring for about 6 hours, the remaining allyl in the reaction solution was removed. When the group was quantified by JR spectrum analysis, it was confirmed that the carbon-carbon double bond of 1645c+s-' had disappeared.Furthermore, toluene and unreacted excess cyclic polysiloxane in the reaction system were removed. In order to do this, vacuum degassing was carried out at 80°C for 3 hours, and approximately 315 g of polypropylene oxide having hydrosilyl groups was turned into a pale yellow,
Obtained as a viscous liquid. Viscosity measured by E-type viscometer is 3
The hydrosilyl group in 8 poise (40°C) was 215 in the IR spectrum.
This was confirmed as strong absorption at 0 cm-'. 300MHz
The NMR spectrum of 5t-C and Si was analyzed.
By comparing the combined peak intensity of CHz- and the peak intensity of 5j-H, the cyclic polysiloxane 1
It was found that an average of 1.31 hydrosilyl groups per molecule were reacted. That is, the polymer is a polypropylene oxide whose molecular weight has been partially increased by a cyclic hydrogen polysiloxane and which has a molecular terminal of the following formula.

Synthesis Example 3 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 THE were placed in a round bottom flask equipped with a stirring bar, a thermometer, a dropping funnel, a nitrogen blowing tube, and a 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 50 d of toluene, washing with 200 d of aqueous hydrochloric acid, neutralizing, and concentrating. The number average molecular weight of the obtained oligomer was determined to be 3,200 by VPO measurement. 3QQMHz 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 4 A 300 d four-bottle flask equipped with a stirring bar, dropping funnel, thermometer, 3-way pot, and cooling tube was prepared.
58600) 34.55g (0,1435mol
) was charged into a flask. 100 g of polycaprolactone synthesized in Synthesis Example 3 and having an average of 2.0 allyl groups in each molecule (moles of olefin: 0.0575 mol)
), toluene 100H1, and chloroplatinic acid catalyst solvent CH
□PtCl&・6LO1g to ethanol1M1.1,2
-60μl of solution dissolved in dimethoxyethane 9mi
A toluene solution consisting of the above 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 the dropwise addition was completed, the remaining allyl group in the reaction solution was quantified by IR spectrometry after stirring at 80°C for about 5 hours, and it was confirmed that the carbon-carbon double bond at 1645 cm-' had disappeared. It was done.

Next, in order to remove the catalyst remaining in the reaction system, 10
was added at room temperature, stirred for 2 hours and filtered using a flash column. In order to remove toluene and excess cyclic polysiloxane, the filtrate was evaporated and devolatilized under reduced pressure at 80°C for 3 hours to obtain a colorless and transparent viscous liquid. The hydrosilyl group in the polycaprolactone was recognized as a strong absorption at 2150 cm-' in the IR spectrum. Furthermore, by comparing the intensity of the Si- and combined peaks of 5i-CHs and 5i-CHz- in an NMR spectrum of 300 MH2, it was found that an average of 1.05 hydrosilyl groups per molecule of the cyclic polysiloxane reacted. I found out that I did it. That is, the polymer is a polycaprolactone whose molecular weight has been partially increased by a cyclic hydrogen polysiloxane and which has a molecular terminal of the following formula.

Synthesis Example 5 of HCHs 50 d of toluene was added to 300 g of hydrogenated polyisobrene having hydrosilyl groups at both ends (manufactured by Idemitsu Petrochemical Co., Ltd., trade name: Meiko Ball) and dehydrated by azeotropic deaeration. Mu-BuO
A solution of 48 g of K in 200 d of THF was injected.

After reacting at 50°C for 1 hour, allyl chloride 41
d was added dropwise over about 30 minutes.After the dropwise addition, the reaction was carried out at 50°C for 1 hour.After the reaction, 30g of aluminum silicate was added to the reaction solution to adsorb the formed salt, and the mixture was stirred at room temperature for 30 minutes. did. By filtration and purification, about 250 g of allyl-terminated hydrogenated polyisobrene was obtained as a viscous liquid. 3
00MHz 'HNMR analysis confirmed that allyl groups were introduced into 92% of the ends. The number of moles of olefin determined from the iodine value is 0°1072 mol/10
It was 0g. The viscosity measured by an E-type viscometer was 302 boids (32°C).

*Typical physical properties of Ebol (from technical data) Hydroxyl group content (weq/g) 0.90 Viscosity (poise)
/30℃) 700 average molecular weight (vpo measurement)
2500 Synthesis Example 6 A 300D four-bottle flask equipped with a stirring bar, dropping funnel, thermometer, 3-way pot, and cooling tube was prepared.
8600) 31.5 g (0,131 mol) was charged into a flask. 50 g (
number of moles of olefin 0,0536 sol), toluene 5
0m, and chloroplatinic acid catalyst solvent (HlPtCli・6H
, Olg dissolved in ethanol ld and 1,2-dimethoxyethane 9d) A toluene solution consisting of 60 μl 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 the completion of the 0 dropwise addition and stirring at 80°C for about 5 hours, the remaining allyl group in the reaction solution was quantified by IR spectroscopy, and it was found that the carbon-carbon double bond at 1645 cm-' had disappeared. Next, to remove the catalyst remaining in the reaction system, silica gel (Wakogel CC-200, manufactured by Wako Pure Chemical Industries, Ltd.) was added at room temperature, stirred for 2 hours, and then transferred to a flash column. It was filtered using In order 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 and transparent viscous liquid. Viscosity measured by E-type viscometer is 5
It was 14 poise (23°C). The hydrosilyl group in the hydrogenated polyisobrene has an IR spectrum of 2150 cm-
' was confirmed as a strong absorption.

In addition, by comparing the intensity of the combined peak of 5t-H and 5i-C and 5i-CH,- with NMR subtractor at 300 MHz, it was found that an average of 1.2 hydrosilyls per molecule of the cyclic polysiloxane. It was found that the group had reacted. That is, the polymer is a hydrogenated polyisobrene having a molecular terminal of the following formula, whose molecular weight has been partially increased by a cyclic hydrogen polysiloxane.

Synthesis Example 7 II equipped with a stirring bar, dropping funnel, thermometer, 3-way pot, and cooling tube! Next, 25.6 g of n-butyl acrylate, 2.52 g of allyl methacrylate were prepared, and 20 d of toluene was prepared under a nitrogen atmosphere.
g5 0.81 g of n-dodecyl mercaptan, 1.0 g of azobisisobutyronitrile.

A toluene solution of a monomer consisting of 100 d of toluene,
The mixture was added dropwise from the dropping funnel over about 1 hour under refluxing toluene, and after the completion of the addition, 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 26 g of a pale yellow viscous liquid oligomer. The Lt number of allyl groups in the polymer was determined by iodometric titration to be 0. .154mol/100g,
From the molecular weight of 3,900 determined by VPO and the number of moles of allyl groups determined by iodometric titration, it was found that on average about 6.0 allyl groups were introduced into one molecule of the polymer.

Synthesis Example 8 A 200Id 4-bottle flask equipped with a stirring bar, dropping funnel, thermometer, 3-way pot, and cooling tube was prepared.
9.26 g (38,5+amo1) of S8600) and 20 ml of toluene were charged into a flask.

10 g of the allyl group-containing acrylic ester polymer synthesized in Synthesis Example 7, chloroplatinic acid catalyst solvent (H!PtC1, 6
HxOI g to ethanol II! i, solution dissolved in 1,2-dimethoxyethane 9d) 16μ! A toluene solution prepared by dissolving 1.
After 0 drops were added into the flask over a period of 80°
The reaction was continued for an additional 2 hours at C.

At this point, the residual allyl group in the reaction solution was quantified by IR spectroscopy, and it was found that the carbon-carbon double bond at 1645 cm-' had disappeared! Approved 0
Next, in order to remove the catalyst remaining in the reaction system, silica gel (Wakogel CC-200, manufactured by Wako Pure Chemical Industries, Ltd.) 2 was added and stirred at room temperature for about 30 minutes, followed by filtration using a flash column.

In order to remove toluene and excess cyclic polysiloxane, the filtrate was evaporated and degassed under reduced pressure at 80°C for 3 hours to obtain a colorless and transparent viscous liquid. Hydrosilyl groups in the acrylic ester polymer were confirmed as strong absorption at 2150 CI-' in the IR spectrum. Furthermore, by comparing the intensity of the 5i-H peak and the combined peak of S 1-CH3 and Si CHt in the 300 MHz NMR spectrum, it was determined that the average number of hydrosilyl groups per molecule of the cyclic polysiloxane was about 1.1. I realized that I had a reaction. That is, the polymer is a hydrosilyl group-containing acrylic ester polymer having a structure as shown in the following formula, in which the molecular weight is partially increased by a cyclic hydrogen polysiloxane.

(HejJ represents the backbone of the polymer.) Example A: Storage stability test (I) Various storage stability improvements were made to the 5i-H group-containing polymer having the main chain skeleton of polypropylene oxide produced in Synthesis Example 2. The agent was added in an amount of 30 equivalents to platinum, and each sample 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 storage stability of the polymer is dramatically improved by adding the stability improver.

Table 1 The storage stability of the 5i-H group-containing polymer having the main chain skeleton was investigated in the same manner as in Example 1. The results are shown in Table 2,
Benzothiazole had the greatest effect.

Table 2 B: Storage stability test (2) Compatibility test of the hydrogenated polyisobrene produced in Synthesis Example 6 with the allyl group-containing organic polymer produced in Synthesis Examples 1 and 3.5.7 and Synthesis Example 2 In order to examine the compatibility of the 5t-H group-containing organic polymer produced in 4.6.8, predetermined amounts of both components were mixed in the combinations shown in Table 3, and after centrifugal defoaming, the mixed state was Observed.

All combinations with the same main chain skeleton had good compatibility. Among the combinations of different skeletons, the polymer of Synthesis Example 5 (hydrogenated polyisobrene main chain) and the polymer of Synthesis Example 4 (polycaprolactone main chain) had good compatibility.

Table 3 5. OX was added to make 10-'mol.

D: Curability test Good compatibility in the compatibility test of C above (A) (B)
In order to examine the curability of the combination of blue components, a chloroplatinic acid catalyst solution [component (C)] was added and mixed well. As the storage stability improver [component (D)], those shown in Table 4 were used.

A portion of the mixture was placed on a gelling tester (manufactured by Nisshin Kagaku), and the snap-up time (time until it becomes rubber elastic) was measured at 100°C. The results are shown in Table 4, and it was found that the composition had fast curing properties at high temperatures.

○: Compatible ×: Not compatible (Note 1) Components (B) and (A) were mixed so that the molar ratio of hydrosilyl group to allyl group was 1/1.

(Note 2) For the catalyst solution, the components (B) and (A) are mixed so that the molar ratio of hydrosilyl group to allyl group (see Table 1) is 1/1 with respect to the alkenyl group of each polymer. Mixed.

(Note 2) The catalyst solution was added to the alkenyl group of the PT polymer at a concentration of 5.0 x 10-' sol. (Note 3) The storage stability improver was added during the synthesis of component (B). 30 to the pt of the catalyst used.

E: Dumbbell physical properties of cured product Alkenyl group-containing organic polymer [component (A)], 5i-H
Predetermined amounts of the group-containing organic polymer [component (B)] and the chloroplatinic acid catalyst solution [component (C)] were stirred and mixed. As the storage stability improver [component (D)], those listed in Table 5 were used.

The mixture was degassed by centrifugation and poured into a polyethylene mold. After degassing again at room temperature and under reduced pressure,
By curing for 1 hour at 0'C, a uniform rubbery cured product with a thickness of 3 m was obtained. From the sheet of the cured product, JIS
A No. 3 dumbbell conforming to K 6301 was punched out and subjected to a tensile test at a tensile speed of 200 am/sin. The results are shown in Table 5.

Table 5 (Note 1) The molar ratio of hydrosilino 4 and alkenyl group is 1/
The (A) component and the (B) component were mixed so that the total amount was 1.

(Note 2) The catalyst solution was added so that pt was 5.0×10'mol based on the alkenyl group of component (A).

(Note 3) The storage stability improver was added in an amount of 30 equivalents to Pt in the catalyst used in the synthesis of component (B).

F: Deep part curability test The deep part curability of the composition used in E above was investigated. That is, these compositions were poured into a polyethylene container with a height of 10 cm and an inner diameter of 1 cm to a height of 5 cm,
After centrifugation and degassing under reduced pressure, it was cured at 100°C for 1 hour. When the IC11 portion was cut out from the bottom of the container and the curability was examined, uniform cured products were obtained for all compositions. From this result, it was found that the composition of the present invention has excellent deep curability.

〔Effect of the invention〕

As mentioned above, according to the present invention, fast curing, deep curing,
It is possible to provide a cured product with excellent mechanical properties and storage stability.

Claims (1)

[Claims] 1. A curable composition with excellent storage stability comprising the following components (A), (B), (C) and (D) as essential components; (A) at least 1 in the molecule; (B) an organic polymer containing at least two hydrosilyl groups in the molecule; (C) a hydrosilylation catalyst; (D) a storage stability improver. 2. The alkenyl group-containing organic polymer as component (A) has a molecular weight of 500 to 50,000, the molecular weight of the hydrosilyl group-containing organic polymer as component (B) is 500 to 50,000, and (A)
2. The composition according to claim 1, wherein the molar ratio of the alkenyl group in the component to the hydrosilyl group in the component (B) is 0.2 to 5.0. 3. The organic polymer of component (A) has the formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [R^1 is the formula -R^2-, -R^3-O-R^ 4-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^2, R^3, R^4 have a carbon number of 1 to 20
A group selected from divalent organic groups represented by divalent hydrocarbon groups), R^5 is hydrogen or a methyl group, and a is an integer of 0 or 1. ] has at least one alkenyl group represented by
The composition according to claim 1 or 2, having a molecular weight of 500 to 50,000. 4. The composition according to claim 1, 2 or 3, wherein the alkenyl group-containing organic polymer of component (A) is a polyether polymer; 5. The alkenyl group-containing organic polymer of component (A) is a polyester. The composition according to claim 1, 2 or 3, which is a polymer. 6. A claim in which the alkenyl group-containing organic polymer of component (A) is selected from the group consisting of polyisobutylene, hydrogenated polyisobrene, hydrogenated polybutadiene, 1,4-polybutadiene, 1,2-polybutadiene, and copolymers thereof. Item 1
, 2 or 3. 7. The alkenyl group-containing organic polymer main chain skeleton of component (A) is at least one selected from ethyl acrylate, butyl acrylate, allyl acrylate, methyl methacrylate, butyl methacrylate, and allyl methacrylate, or selected from the above acrylates and methacrylates. Claims 1 and 2 are acrylic ester polymers obtained by radical polymerization of at least one monomer component selected from styrene, vinyl acetate, and acrylonitrile that can be copolymerized with these.
Or the composition according to 3. 8. The hydrosilyl group-containing organic polymer of component (B) has the formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) _3 and carbon number is 1~
It is a group selected from 10 organic groups, and each R may be the same or different. ) Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (m≧1, m+n=
2-50) (R is the same as above) A substituent containing at least one hydrosilyl group. R^1 is the formula -R^2-, -R^3-O-R^4-, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ (in the formula, R ^2, R^3, R^4 have 1 to 20 carbon atoms
a is an integer of 0 or 1; a is an integer of 0 or 1; ] The composition according to claim 1 or 2, which has at least one hydrosilyl group represented by the following and has a molecular weight of 500 to 50,000. 9. The hydrohylyl group-containing organic polymer of component (B) has the formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II)
From the group consisting of (p, q are 0 or positive integers satisfying 2≦p+q≦4) The selected group, R^1, has the formula -R^2-, -R
^3-O-R^4-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^
2, R^3, and R^4 are groups selected from divalent organic groups represented by divalent hydrocarbon groups having 1 to 20 carbon atoms, and a is an integer of 0 or 1. ] The composition according to claim 1 or 2, which has at least one hydrosilyl group represented by the following and has a molecular weight of 500 to 50,000. 10. The composition according to claim 1, 2, 8 or 9, wherein the hydrosilyl group-containing organic polymer of component (B) is a polyether polymer. 11. The composition according to claim 1, 2, 8 or 9, wherein the hydrosilyl group-containing organic polymer of component (B) is a polyester polymer. 12. The composition according to claim 1, 2, 8 or 9, wherein the hydrosilyl group-containing organic polymer of component (B) is a hydrocarbon polymer. 13. The composition according to claim 1, 2, 8 or 9, wherein the hydrosilyl group-containing organic polymer of component (B) is an acrylic acid ester polymer. 14. The hydrosilyl group-containing organic polymer of component (B) is (
The composition according to claim 1, 2, 8 or 9, which has good compatibility with the alkenyl group organic polymer of component A). 15. Component (B) is produced by reacting an organic polymer containing at least one alkenyl group in the molecule with a polyhydrosilane compound in the presence of a hydrosilylation catalyst so that the hydrosilyl group remains. Molecular weight is 500~
The composition according to claim 1 or 2, which is a hydrosilyl group-containing organic polymer having a molecular weight of 50,000. 16. Component (B) is a hydrosilyl group-containing organic polymer whose molecular weight has been increased by reacting two or more hydrosilyl groups of some polyhydrosilane compounds with alkenyl groups of an organic polymer. Composition. 17, the storage stability improver of component (D) is a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound,
The composition according to claim 1 or 2, which is selected from nitrogen-containing compounds, tin-based compounds, organic peroxides, and mixtures thereof. 18. Claim 1 or 2, wherein the storage stability improver of component (D) is selected from dimethyl malate, dimethyl acetylene dicarboxylate, 2-pentenenitrile, benzothiazole, 2,3-dichloropropene, quinoline, and mixtures thereof. 2. Composition according to item 2.