JP3256511B2 - Curing agent, method for producing the same, and curable composition using the curing agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a cured product having a hydrosilyl group other than an optically crosslinked siloxane polymer.
The present invention relates to an organic curing agent to be a cured product, a method for producing the same, and a curable composition using the curing agent.

[0002]

2. Description of the Related Art Conventionally, various curable liquid compositions which cure to form a rubber-like substance have been developed. Above all, as a curing system excellent in deep curing, a polyorganosiloxane having an average of two or more vinyl groups in one molecule at the terminal or in the molecular chain, and a hydrogen atom bonding to a silicon atom 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 converted into a polyorganohydrogensiloxane by phase separation. Hydrolysis and dehydrocondensation reactions are promoted, and there is a problem that sufficient mechanical properties cannot be obtained due to voids.

[0003]

Means for Solving the Problems The present invention solves these problems as a result of intensive studies in view of the above circumstances, and is a curable liquid composition which is fast-curing and excellent in deep-part curability.
An object of the present invention is to provide an organic curing agent having a hydrosilyl group in a molecule and a method for producing the same, which are suitable for providing the composition.

[0004] That is, instead of the polyorganohydrogensiloxane has been used in the curing reaction by a conventional hydrosilylation, using at least two organic-based curing agent you containing hydrosilyl groups in a molecule, containing an alkenyl group When the organic polymer 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 curability and having sufficient tensile properties can be obtained. in addition, it is possible to use an alkenyl group-containing organic polymer having any kind of main chain skeleton, very to be able to create a cured product that can be applied to a wide range of applications, further the organic curing agent is generally a low viscosity Having been found to be advantageous in performing work at the time of preparing a cured product, and arrived at the present invention.

A first aspect of the present invention is a non-polymeric organic curing agent having preferably at least two hydrosilyl groups in the molecule, that is, the general formula (IX):

[0006]

Embedded image

Wherein R ⁵ is a hydrocarbon group having 1 to 50 carbon atoms, R ⁸ is a hydrogen atom or a methyl group, and a compound (A3) having a hydrocarbon represented by the following formula: silicon compound (B) and the hydrosilyl group mixture was reacted in the presence of a hydrosilylation catalyst to contain hydrosilyl groups was prepared as residual, curative and organic systems ing of the alkenyl group-containing organic polymer A curing agent, the polyvalent hydrogen silicon compound (B) is
_{H 3) 2 SiH 2, (} C 6 H 5) 2 SiH 2, CH 3 SiH 3,
C ₆ H ₅ SiH ₃ , (C ₂ H ₅ ) ₂ SiH ₂ , CH ₃ (CH ₂ ) ₅
A monosilane compound represented by SiH ₃ ;

[0008]

Embedded image

A polysilicon compound represented by the formula:

[0010]

Embedded image

[0011]

Embedded image

[0012]

Embedded image

At least one compound selected from the group consisting of linear, branched and cyclic polyvalent hydrogenpolysiloxanes, wherein the alkenyl group-containing organic polymer is a polyester polymer, Acrylic ester-based polymer, acrylic ester-based copolymer,
An organic polymer containing at least one alkenyl group in a molecule selected from the group consisting of a hydrocarbon polymer, a polycarbonate polymer, a polysulfide polymer, a polyamide polymer, and a diallyl phthalate polymer.
The cured product is a cured product other than the optically crosslinked siloxane polymer.
Object and name Ru organic curing agent (Claim 1), polyvalent hydrogensilicon compound of the component (B),

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

The organic curing agent according to claim 1, which is at least one compound selected from the group consisting of linear, branched and cyclic polyvalent hydrogenpolysiloxanes represented by (B) Component polyvalent hydrogen silicon compound,

[0018]

Embedded image

The organic curing agent according to claim 1, which is at least one compound selected from the group consisting of the following, and the polyvalent hydrogen silicon compound as the component (B):

[0020]

Embedded image

The organic curing agent according to claim 1, which is at least one compound selected from the group consisting of (Claim 4), and R in the compound (A3) represented by the general formula (IX).
⁵ is

[0022]

Embedded image

The organic curing agent according to claim 1, which is a monovalent group selected from the group consisting of (1), (2), (3) and (4), represented by the general formula (IX) according to (1) compound (A3), containing claim 1, wherein the polyvalent hydrogensilicon compound (B) and a hydrosilyl group in which hydrosilyl group mixture was reacted in the presence of a hydrosilylation catalyst was prepared as the remaining claims The method for producing an organic curing agent according to claim 1 (claim 6), wherein the component (B) is the compound described in claim 2, the production method according to claim 6 (claim 7), and the component (B) The production method according to claim 6, which is the compound described in claim 3, (claim 8), and the production method according to claim 6, wherein component (B) is the compound described in claim 4. The following components (C), (D) and (E) are essential Containing a minute, the cured product for optical
A curable composition that becomes a cured product other than the crosslinked siloxane polymer ; (C) the organic curing agent according to claim 1, 2, 3, 4, or 5, (D) a polyester polymer, an acrylate polymer, At least one alkenyl group in a molecule selected from the group consisting of an acrylate copolymer, a hydrocarbon polymer, a polycarbonate polymer, a polysulfide polymer, a polyamide polymer, and a diallyl phthalate polymer An organic polymer containing: (E) a hydrosilylation catalyst (Claim 10);
The curable composition according to claim 10, which is the organic curing agent described in claim 11, wherein the molar ratio of the hydrosilyl group to the alkenyl group of the component (C) and the component (D) is from 0.2 to 5 in molar ratio. The curable composition according to claim 10 or claim 11, wherein the component (C) is the organic curing agent according to claim 2. Item 13), The curable composition according to Item 10 or 12, wherein the component (C) is the organic curing agent according to Item 3, and Component (C) is the organic curing agent according to Item 4. The curable composition according to claim 10 or claim 12 which is an agent, wherein the molecular weight of the organic polymer of component (D) is 5
10. The composition of claim 10, 11, 12, 1, or 100.
The curable composition according to claim 3, 14, or 15 (claim 1)
6), wherein the alkenyl group of the organic polymer of the component (D) is present at the molecular terminal.
The curable composition according to 5 or 16 (Claim 17),
The organic polymer of the component (D) is an organic polymer selected from the group consisting of a polyester polymer, an acrylate polymer, an acrylate copolymer, a hydrocarbon polymer, and a polycarbonate polymer. Claims 10 and 1
The curable composition according to 1, 12, 13, 14, 15, 16 or 17 (claim 18), wherein the component (C) is the organic curing agent according to claim 5, and the organic component (D) 10. The polymer according to claim 10, wherein the polymer is a hydrocarbon polymer.
The curable composition according to claim 19, wherein the organic polymer of the component (D) is a saturated hydrocarbon polymer (claim 19). (20) The organic polymer of the component (D) is an ethylene-propylene copolymer, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, isoprene, or a copolymer of butadiene with acrylonitrile, styrene, or the like. The curable composition according to claim 20, which is a polyolefin-based polymer obtained by addition (claim 21),
The organic polymer (D) is an acrylate polymer and / or an acrylate copolymer obtained by using a vinyl monomer having an alkenyl group as a copolymerizable monomer. ,
11, 12, 13, 14, 15, 16, 17 or 18
22. The curable composition according to claim 22, wherein the organic polymer of the component (D) reacts with a hydroxyl group in an acrylate polymer and / or acrylate copolymer having a hydroxyl group at a terminal or a side chain. And a polymer obtained by reacting a compound having both a functional group and an alkenyl group.
The present invention relates to the curable composition according to 5, 16, 17 or 18 (claim 23).

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The molecule according to the first aspect of the present invention preferably contains at least two hydrosilyl groups in the molecule.
And the cured product is other than the optically crosslinked siloxane polymer.
The organic curing agent goods and ing, those described below are exemplified. Specific examples of a group containing a hydrosilyl _{group, -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,

[0025]

Embedded image

A group containing two or more silicon atoms, such as

[0027]

Embedded image

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; A positive integer and 2 ≦ m + n ≦ 50), a general formula:

[0029]

Embedded image

Wherein 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), general formula:

[0031]

Embedded image

Wherein R is the same as above, m is a positive integer,
n is 0 or a positive integer, and includes various chain, branched, and cyclic polyvalent hydrogensiloxane groups represented by 2 ≦ m + n ≦ 50).

Of the above various hydrosilyl-containing groups,
From the viewpoint that the compatibility of the hydrosilyl group-containing organic curing agent of the present invention with various organic polymers is unlikely to be impaired, the molecular weight of the group constituting the hydrosilyl group is 50.
It is desirably 0 or less, and the following are preferable in consideration of the reactivity of the hydrosilyl group.

General formula:

[0035]

Embedded image

(Where p is a positive integer, q is 0 or a positive integer, and 2 ≦ p + q ≦ 4)

[0037]

Embedded image

When two or more hydrosilyl-containing groups are present in the same molecule, they may be the same or different.

Contains a hydrosilyl group, and the cured product is optical
It is sufficient two to preferably at least during 1 molecule for the number of hydrosilyl groups of the total contained in the cured product other than the crosslinked siloxane polymeric Do that organic curing agent, but preferably 2 to 15, 3 to 12 Individuals are particularly preferred. When the hydrosilyl group-containing organic curing agent of the present invention is mixed with various alkenyl group-containing organic polymers in the presence of a hydrosilylation catalyst and cured by a hydrosilylation reaction, the number of hydrosilyl groups is 2 When the number is less than the number of pieces, the curing is slow, and the curing failure often occurs. If the number of the hydrosilyl groups is more than 15, the stability of the curing agent will be poor, and a large amount of hydrosilyl groups will remain in the cured product even after curing, causing voids and cracks.

The hydrosilyl group is represented by the formula (II): XR ^2- (II) (wherein X is a substituent containing at least one hydrosilyl group, and R ² is A divalent hydrocarbon group having 2 to 20 carbon atoms, which may contain one or more ether bonds).

More specifically, general formula (V): X _a -R ^5a (V) wherein X is a group containing at least one hydrosilyl group, and R ^5a is preferably a group having 2 to 2 carbon atoms. (A is an integer selected from 1 to 4), wherein the main chain skeleton is a compound represented by the formula: Note that a =
Case 1 is an example of the organic curing agent of the present invention.

In the general formula (V), R ^5a represents a monovalent to tetravalent hydrocarbon group having 2 to 50 carbon atoms.

[0043]

Embedded image

[0044]

Embedded image

And the like.

Of these,-(CH ₂ ) _n- (n =
2-10),

[0047]

Embedded image

Is preferred. Further,-(CH ₂ ) _n- (n =
2 to 10) are particularly preferred.

The method for producing the hydrosilyl group-containing organic curing agent is not particularly limited, and any method may be used. For example, (i) a method of treating an organic compound having a Si—Cl group in a molecule 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) A) reacting an organic compound having a functional group X in the molecule with a compound having a functional group Y and a hydrosilyl group simultaneously reacting with the functional group in the molecule;
(Iii) A method in which a polyhydrosilane compound having at least two hydrosilyl groups is selectively hydrosilylated 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 is considered. .

The second invention of the present invention relates to the method (iii) for producing a hydrosilyl group-containing organic curing agent. That is, the organic compound (A) containing one alkenyl group in the molecule and the polyvalent hydrogen silicon compound (B)
DOO reacted in the presence of a hydrosilylation catalyst, and hydrosilyl group is characterized by reacting to remain even after the reaction, the cured product other than the optical cross-linking siloxane polymer hardness
The present invention relates to a method for producing a hydrosilyl group-containing organic curing agent which is a compound.

As the component (A), various hydrocarbon compounds containing an alkenyl group can be used.

The hydrocarbon compound used as the component (A) is represented by the general formula (IX):

[0053]

Embedded image

(Wherein R ⁵ is a hydrocarbon group having 1 to 50 carbon atoms, and R ⁸ is a hydrogen atom or a methyl group). General formula (I
In X), R ⁵ is the same as in the case where R ^5a in the general formula (V) is monovalent.

The polyvalent hydrogen silicon compound (B) used in the present invention includes (CH ₃ ) ₂ S
iH ₂ , (C ₆ H ₅ ) ₂ SiH ₂ , CH ₃ SiH ₃ , C ₆ H ₅ S
iH ₃ , (C ₂ H ₅ ) ₂ SiH ₂ , CH ₃ (CH ₂ ) ₅ SiH ₃
A monosilane compound represented by the formula:

[0056]

Embedded image

A polysilicon compound such as

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

Various chain, branched and cyclic polyvalent hydrogen polysiloxanes represented by
The number of hydrosilyl groups in one molecule of the polyvalent hydrogen silicon compound (B) is preferably 2 to 16,
Particularly, 3 to 13 are preferable. In addition, since the compatibility of the hydrosilyl group-containing organic curing agent of the present invention produced from the component (A) and the component (B) is hardly impaired, the polyvalent hydrogen silicon compound of the component (B) The molecular weight is preferably 500 or less. Furthermore, from the viewpoint that the reactivity at the time of the hydrosilylation reaction between the component (A) and the component (B) described later is high,

[0062]

Embedded image

Is preferred. Furthermore, since the unreacted components are easily removed under reduced pressure after the hydrosilylation reaction,

[0064]

Embedded image

Is preferred.

The cured product of the present invention may be a crosslinked siloxane polymer for optical use.
A hydrosilyl group-containing organic curing agent that is a cured product other than a limer is produced by a hydrosilylation reaction between an alkenyl group-containing organic compound (A) and a polyvalent hydrogen silicon compound (B). The catalyst used at this time is, for example, a substance in which solid platinum is supported on a carrier such as simple substance of platinum, alumina, silica, carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. And a platinum-olefin complex {for example, Pt (CH ₂ CH ₂ ) ₂ (PP
_{h 3) 2 Pt (CH 2} = CH 2) 2 Cl 2}; platinum - vinylsiloxane complex {for example, Pt _n (ViMe ₂ SiOSi
Me ₂ Vi) _m , Pt [(MeViSiO) ₄ ] _m }; platinum-phosphine complex {for example, Pt (PPh ₃ ) ₄ , Pt
(PBu ₃ ) ₄ {; platinum-phosphite complex}
Pt [P (OPh ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ } (where 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, and also the platinum-hydrocarbon complexes described in Ashby U.S. Pat. Nos. 3,159,601 and 3,159,662; and Lamoreau
x) Platinum alcoholate catalysts described in U.S. Pat. No. 3,220,972. Also useful are the platinum chloride-olefin complexes described in Modic U.S. Pat. No. 3,516,946. Examples of catalysts other than platinum compounds include RhC
l (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuC
l ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl _2.
2H ₂ O, NiCl ₂ , TiCl _{4 and the} like (P
h represents a phenyl group). These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferable.

The amount of the catalyst is not particularly limited, but is preferably in the range of 10 ^-1 to 10 ^-8 mol based on the alkenyl group in the component (A). Preferably 10 ^-3 to 10 ^-6 mol
It is good to use within the range.

In the hydrosilylation reaction, the use of a solvent is not particularly required. However, when the starting material is a solid or high-viscosity one and the operation such as stirring is difficult, an inert organic solvent is appropriately used. 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; and ketone solvents such as methyl ethyl ketone. Solvents and halogenated hydrocarbon solvents such as trichloroethylene are exemplified.

As to the method of adding both components (A) and (B) and the hydrosilylation catalyst used in the present invention, the three components are charged at once, and the component (B) is added to the component (A) and the hydrosilylation catalyst. A method of adding the component (B) to the component (A) and the hydrosilylation catalyst,
A method of adding the component (A) to the component (B) and the catalyst, a method of simultaneously adding the components, and the like can be considered, but there is no particular limitation. In order to make the reaction such that the hydrosilyl group remains even after the reaction, it is considered that it is desirable that the polyvalent hydrogen silicon compound as the component (B) is always present in excess with respect to the component (A). A preferred method is to add a mixture of the alkenyl group-containing organic compound as the component (I) and the hydrosilylation catalyst to the polyvalent hydrogen silicon compound as the component (B). The reaction temperature is 0 to 200 ° C, preferably 50 to 150 ° C. If the reaction temperature is lower than 0 ° C., the catalytic activity is not sufficient, and the reaction rate is reduced. When the temperature is higher than 150 ° C., the catalyst is often deactivated.

The hydrosilyl group-containing organic curing agent obtained by the above-described method usually contains a hydrosilylation catalyst even after the reaction, so that its stability is generally not good. In some cases, the Si—H group Si—
Conversion to OH groups occurs and phenomena such as an increase in viscosity and gelation are observed. Therefore, after the hydrosilylation reaction, it is desirable to remove the catalyst from the hydrosilyl group-containing organic curing agent. Examples of the removal method include a method of stirring and column-treating the reaction solution with silica, silica gel, alumina, an ion exchange resin, or the like, and a method of washing with a neutral or weakly acidic aqueous solution.

The hydrosilyl group-containing organic curing agent thus obtained generally has better compatibility with organic polymers than known hydrosilyl group-containing polysiloxanes. Therefore, if the hydrosilyl group-containing organic curing agent of the present invention and the alkenyl group-containing organic polymer are mixed and cured in the presence of the above-mentioned various hydrosilylation catalysts, the compatibility of these two components is obtained. , A uniform cured product can be obtained without a phenomenon such as foaming. The curing conditions are not particularly limited, but are generally 0 to 20.
Curing at 0 ° C, preferably 50 to 150 ° C, for 10 seconds to 4 hours is good. Especially at high temperatures of 80-150 ° C.
Some curable in a short time of about 30 seconds to 30 minutes. Further, even if a cured product having a thickness of, for example, 1 cm or more is produced by the above-described method, a cured product which is uniformly cured and has excellent deep curability can be obtained. The properties of the cured product depend on the curing agent used, the main chain skeleton and the molecular weight of the organic polymer, and the like, but can be prepared from rubbery to resinous.

In preparing a cured product, in addition to the three main components of a hydrosilylation catalyst, a hydrosilyl group-containing organic curing agent and an alkenyl group-containing organic polymer, various solvents, plasticizers, fillers, A pot life extender, a pigment, an antioxidant, an ultraviolet absorber, an adhesion promoter and the like may be optionally used.

The third invention of the present invention comprises the following components (C), (D) and (E) as essential components ,
The present invention relates to a curable composition whose product is a cured product other than the optically crosslinked siloxane polymer .

(C) the organic curing agent according to claim 1, 2, 3, 4 or 5, (D) an organic polymer containing at least one alkenyl group in the molecule, and (E) a hydrosilylation catalyst.

The organic curing agent according to any one of claims 1, 2, 3, 4 and 5, which preferably contains at least two hydrosilyl groups in the molecule as component (C) of the present invention,
Various hydrocarbon-based curing agents described in the first invention can be used. Preferred molecular weight, molecular structure of the curing agent,
The structure of the hydrosilyl group and the number per molecule are the same as in the description of the first invention of the present invention.

The method for producing the component (C) is not particularly limited, but is preferably produced by the method of the second invention of the present invention.

As the organic polymer having at least one alkenyl group in the molecule as the component (D) of the present invention, those having various main chain skeletons as described below can be used.

To be more specific, polyester-based polymers, ethylene-propylene-based copolymers, polyisobutylene, isobutylene obtained by condensation of dibasic acid such as adipic acid and glycol or ring-opening polymerization of lactones And copolymers with isoprene, polychloroprene, polyisoprene, copolymers with isoprene and butadiene, acrylonitrile, styrene, polybutadiene, butadiene and styrene, copolymers with acrylonitrile, etc., polyisoprene, polybutadiene, isoprene or Polyolefin-based polymers obtained by hydrogenating copolymers of butadiene with acrylonitrile, styrene, etc .; polyacrylates obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate; Rate, acrylic acid esters and vinyl acetate such as butyl acrylate, acrylonitrile,
Methyl methacrylate, acrylate copolymer with styrene, etc., graft polymer obtained by polymerizing vinyl monomer in the organic polymer, polysulfide 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 by condensation polymerization of ε-aminoundecanoic acid, Nylon 12 by ring-opening polymerization of ε-aminolaurolactam A polyamide-based polymer such as copolymerized nylon having two or more components among the above-mentioned nylons, for example, bisphenol A
And a polycarbonate polymer and a diallyl phthalate polymer produced by condensation polymerization from carbonyl chloride. Among the polymers having the main chain skeleton, the polyester-based polymer, the acrylate-based polymer, and the acrylate-based polymer are preferred in that the compatibility of the component (C) with the hydrosilyl group-containing organic curing agent is good. Polymers, hydrocarbon polymers and polycarbonate polymers are preferred. Further, it is particularly preferable that the combination of both components (C) and (D) is a combination of a hydrocarbon-based curing agent and a hydrocarbon-based polymer.

The alkenyl group in the component (D) is not particularly limited, but has the general formula (XI):

[0080]

Embedded image

(Wherein R ¹ is a hydrogen atom or a methyl group)
An alkenyl group represented by is preferred.

An alkenyl group is introduced into the organic polymer,
Various methods can be used for the component (D), and can be roughly 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 the polymerization, for example, an organic polymer having a functional group such as a hydroxyl group or an alkoxide group at a terminal, main chain or side chain may be added to an active group having a reactivity with the functional group. And an organic compound having an alkenyl group, whereby the alkenyl group can be introduced into the terminal, main chain or side chain. Examples of the organic compound having an active group and an alkenyl group that are reactive to the functional group include C ₃ -C ₂₀ unsaturated such as acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride, and acrylic acid bromide. Fatty acids, acid halides, acid anhydrides and allyl chloroformate (CH
₂ = CHCH ₂ OCOCl), C ₃ -C ₂₀ unsaturated fatty acid-substituted carbonates such as allyl bromoformate (CH ₂ ＣＨCHCH ₂ OCOBr), allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloro) Methyl) benzene, allyl (bromomethyl)
Benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ether, 1-hexenyl (chloromethoxy) benzene, allyloxy (chloromethyl) benzene and the like can be mentioned.

As a method for introducing an alkenyl group during the polymerization, for example, when an organic polymer of the component (D) is produced by a radical polymerization method, low radical reactivity is present in molecules such as allyl methacrylate and allyl acrylate. An alkenyl group can be introduced into the main chain or the terminal of the polymer by using a radical chain transfer agent having an alkenyl group having a low radical reactivity such as a vinyl monomer having an alkenyl group or an allyl mercaptan. When preparing a rubber-like cured product using the composition of the present invention,
It is preferable that the alkenyl group of the component (D) be present at the molecular terminal because the effective network chain length of the cured product becomes longer.

There is no particular limitation on the mode of bonding between the alkenyl group and the organic polymer. In addition to the case where the alkenyl group is directly bonded by a carbon-carbon bond, ether, ester, carbonate,
Examples include those in which the alkenyl group is bonded to the main chain skeleton of the organic polymer via an amide or urethane bond.

The molecular weight of the component (D) is determined by considering the properties of the cured product and the compatibility with the component (C).
50,000 to 50,000 are preferable, and 500 to 20,000 are particularly preferable. The number of alkenyl groups is preferably 2 to 5 on average in one molecule.

The ratio of the hydrosilyl group to the alkenyl group of the component (C) and the component (D) produced as described above is preferably 0.2 to 5.0 in terms of molar ratio, more preferably 0.4 to 5.0.
-2.5 is particularly preferred. When the molar ratio is less than 0.2, when the composition of the present invention is cured, curing is insufficient, and only a cured product with a low tackiness and stickiness is obtained.
When the molar ratio is more than 5.0, a large amount of active hydrosilyl groups remain in the cured product even after curing, so that cracks and voids are generated, and a uniform and strong cured product tends not to be obtained.

The hydrosilylation catalyst which is the component (E) of the present invention is not particularly limited, and any catalyst can be used.

Specifically, the same catalyst as that used in the production of the hydrosilyl group-containing organic curing agent according to the second invention of the present invention can be used. 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 complex and the like are preferable. 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 (D). Preferably, it is used in the range of 10 ^-3 to 10 ^-6 mol.

If the composition of the present invention is prepared by mixing the components (C), (D) and (E) and then cured, the composition has excellent deep curability without causing phenomena such as foaming. A cured product is obtained. The curing conditions are not particularly limited, but are generally 0 to 200 ° C, preferably 30 to 1 ° C.
It is preferable to cure at 50 ° C. for 10 seconds to 4 hours. Especially 80
At a high temperature of up to 150 ° C., some cure in a short time of about 10 seconds to 1 hour. Use the properties of the cured product (C)
Although it depends on the main chain skeleton, molecular weight, etc. of the polymer of the component and the component (D), it can be produced from a rubbery material to a resinous material.

In preparing a cured product, the component (C)
In addition to the three essential components (D) and (E), a solvent, an adhesion improver, a physical property modifier,
Storage stability improvers, plasticizers, fillers, antioxidants, ultraviolet absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, amine radical chain inhibitors, phosphorus peroxide decomposers, Various additives such as a lubricant, a pigment, and a foaming agent can be appropriately added.

[0092]

The present invention will be described below in more detail with reference to specific examples, but the present invention is not limited by these.

Synthesis Example 1 114 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.

[0094]

Embedded image

7.78 g (25 mmol) were added. A solution in which 242 g (2.0 mol) of allyl bromide was dissolved in 300 ml of toluene was gradually dropped from the dropping funnel into 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, so the heating and stirring were stopped. 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 matter by evaporation, the residue was dried under reduced pressure at 80 ° C. for 2 hours to obtain a pale yellow viscous liquid 14.
6 g (95% yield) were obtained. This viscous liquid was identified by elemental analysis, 300 MHz ¹ H-NMR, IR spectrum, etc., as a diallyl ether of bisphenol A:

[0096]

Embedded image

Was confirmed.

IR analysis (neat, cm ^-1 ): 3070
(M, ν = _CH ), 3030 (m), 2960 (S),
2920 (S), 2860 (S) (ν _CH ), 1645
(M, ν _{C = C} ), 1620 (S), 1520 (S), 1
290 (S), 1235 (S), 1180 (S), 10
25 (S), 1000 (S), 920 (S), 825
(S) ¹ H-NMR analysis (300 MHz): See FIG.

Synthesis Example 2 According to the method disclosed in JP-A-53-134095, polyoxypropylene having an allylic olefin group at the terminal was synthesized.

Polyoxypropylene glycol having an average molecular weight of 3000 and powdered sodium hydroxide 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 is 7960
From the iodine value, 92% of the terminals were olefin groups (0.0231 mol / 100 g). The viscosity measured by an E-type viscometer was 130 poise (40 ° C.).

Synthesis Example 3 A 1-L four-necked flask equipped with a stirring rod, a dropping funnel, a thermometer, a three-way cock, and a condenser was prepared.
Polytetramethylene oxide having a hydroxyl group at 000 (trade name: Teratan-2000, manufactured by DuPont)
300 g were charged in the flask. After azeotropic degassing with toluene, 50.5 g of tBuOK was added to THF.
What was dissolved in 200 ml was added. After stirring at 50 ° C. for 1 hour, 49 ml of allyl chloride was added dropwise from the dropping funnel over 1 hour. Approx. 1 at 50 ° C after dropping
After reacting for 30 hours, 30g of aluminum silicate at room temperature
Was added and stirred for 30 minutes. The mixture was filtered using diatomaceous earth as a filter aid, and volatile components were removed by evaporation to obtain about 230 g of a transparent viscous liquid. The product crystallized to a white solid upon standing overnight at room temperature. Iodine value titration (0.0718mo
1/100 g), it was found that an allyl group was introduced into about 73% of the terminals of this polytetramethylene oxide.

Synthesis Example 4 50 ml of toluene was added to 300 g of hydrogenated polyisoprene having hydroxyl groups at both ends (trade name: Epol ^* , manufactured by Idemitsu Petrochemical Co., Ltd.), and the mixture was dehydrated by azeotropic degassing. t-B
A solution prepared by dissolving 48 g of uOK in 200 ml of THF was injected. After reacting at 50 ° C. for 1 hour, 47 ml of allyl chloride was added dropwise over about 30 minutes. After completion of the dropwise addition, the reaction was carried out at 50 ° C. for 1 hour. After the reaction is completed, 30 g of aluminum silicate is added to the reaction solution to adsorb the generated salt.
Was added and stirred at room temperature for 30 minutes. About 2
50 g of allyl-terminated hydrogenated polyisoprene were obtained as a viscous liquid. By 300 MHz ¹ H-NMR analysis, it was confirmed that an allyl group was introduced at 92% of the terminal. The number of moles of the olefin determined from the iodine value is 0.10
It was 46 mol / 100 g. The viscosity measured by an E-type viscometer was 302 poise (23 ° C.).

* Representative physical properties of Epol (from technical data) Hydroxyl content (meq / g) 0.90 Viscosity (poise / 30 ° C.) 700 Average molecular weight [VPO measurement] 2500

Synthesis Example 5 115.72 g of n-butyl acrylate, 60.00 g of methyl methacrylate, 20.1 g of allyl methacrylate
6 g, n-dodecyl mercaptan 6.46 g, azobisisobutyronitrile 2.0 g, toluene toluene solution of acrylate monomer consisting of toluene 400 ml
0 ml of toluene was dropped into the refluxed flask under a nitrogen atmosphere from a dropping funnel over about 2 hours. After the completion of the dropwise addition, the reaction was further continued for 2 hours. The reaction solution was evaporated and further dried under reduced pressure at 80 ° C. for 3 hours to obtain about 195 g of a pale yellow viscous liquid oligomer.
The number of moles of the allyl group determined by iodine titration was 0.0818 m.
ol / 100 g, molecular weight by VPO was 2950, and it was found that an average of 2.4 allyl groups were introduced per molecule.

Synthesis Example 6 300 g (0.1 mol) of polycaprolactone having a terminal hydroxyl group (number-average molecular weight: 3,000, hydroxyl equivalent: 1500), 2
4.0 g of pyridine and 300 ml of THF were charged into a round-bottomed flask equipped with a stir bar, a thermometer, a dropping funnel, a nitrogen blowing tube, and a cooling tube.
g of allyl chloroformate was slowly added dropwise. Then 50
C. and stirred for 3 hours. After removing the generated salt by filtration, 150 ml of toluene was added, and the mixture was washed with 200 ml of an aqueous hydrochloric acid solution, neutralized and concentrated to obtain an allyl-terminated polycaprolactone. VPO of the obtained oligomer
From measurement, the number average molecular weight was 3,200. 300MH
The introduction of the allyl group was confirmed from the spectrum of the olefin portion of the NMR of z. Further, it was confirmed from the quantification of the olefin by iodine titration that an average of 1.83 allyl-type unsaturated groups (0.0573 mol / 100 g) were introduced in one molecule.

Reference Example 1 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, cyclic hydrogen polysiloxane

[0108]

Embedded image

(LS8600, manufactured by Shin-Etsu Chemical Co., Ltd.)
12.03 g (50 mmol) and 20 ml of toluene
Was charged into the flask. 6.16 g (20 mmol) of bisphenol A diallyl ether synthesized in Synthesis Example 1
l), chloroplatinic acid catalyst solvent solution (H ₂ PtCl ₆ · 6H ₂
41 μl of 1.0 g of O dissolved in 9 g of ethanol / 1,2-dimethoxyethane (1/9 V / V) was dissolved in 50 ml of toluene, mixed well, and then charged into a dropping funnel. At 70 ° C., the toluene solution was dropped into the flask over 1.5 hours. When the reaction was further performed at 80 ° C. for 5 hours, an IR spectrum was taken.
The reaction was terminated at this point because the absorption derived from the olefin at 5 cm ^-1 had completely disappeared. The reaction mixture was evaporated to remove volatiles and the residue
After adding 1 hexane to completely dissolve, the mixture was filtered to remove the catalyst. Hexane was distilled off under reduced pressure, and then dried under reduced pressure at 80 ° C. for 1 hour to obtain 12.0 g of a pale yellow viscous liquid. This viscous liquid is 300 MHz ¹ H-NM
Identification by R, IR spectra, and the like revealed that the compound was a Si-H group-containing ether-based curing agent having the following structural formula.

[0110]

Embedded image

By comparing the calculated intensity ratio with the proton intensity ratio (actually measured value of 0.223) of Si—H and Si—CH _{3 in the} 300 MHz ¹ H-NMR spectrum, when n = 0: 6/24 = 0.25 n = 1: 8/36 = 0.222 n = 0 (MW = 789.4) of the curing agent is 4 on average
%, N = 1 (MW = 1338.3). Based on this, the number of Si—H groups in the unit weight was calculated to be 0.604 mol / 100 g.

IR analysis (neat, cm ^-1 ): 3030
(W), 2960 (S), 2920 (S), 2860
(S), 2160 (S, ν _Si-H ), 1605 (m), 1
505 (S), 1255 (S), 1070 (bs) ¹ H-NMR analysis (300 MHz): See FIG.

Reference Example 2 In order to examine the compatibility between the Si-H group-containing ether-based curing agent produced in Reference Example 1 and various allyl group-containing organic polymers having a main chain skeleton, as shown in Table 1, In the combination, a predetermined amount of the curing agent 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. It was found that the Si-H-containing ether-based curing agent had good compatibility with various organic polymers.

Next, in order to examine the curability, a predetermined amount of a 10-fold diluted solution of the chloroplatinic acid catalyst solution used in Reference Example 1 was added to each of the above mixtures and mixed well. A part of the mixture is placed on a gelation tester (manufactured by Nissin Kagaku Co., Ltd.),
At a predetermined temperature, a snap-up time (time until the rubber elasticity is developed) was measured. The results are shown in Table 1, and it was found that the composition was high-temperature fast-curing.

[0115]

[Table 1]

Reference Example 3 A predetermined amount of the Si-H group-containing ether-based curing agent produced in Reference Example 1, 9.54 g of various allyl group-containing polymers produced in Synthesis Examples 2 to 5, and used in Reference Example 1. The chloroplatinic acid catalyst solution was mixed well at the ratio shown in Table 2. The mixture was defoamed by centrifugation and poured into a polyethylene mold. After defoaming again under reduced pressure at room temperature,
By curing for a time, a uniform rubbery cured product having a thickness of about 3 mm was obtained. JIS K from the sheet of the cured product
No. 3 dumbbell according to No. 6301 was punched out and a tensile test was performed at a tensile speed of 200 mm / min. Table 3 shows the results.

From Table 3, it was found that the use of the above-mentioned hydrosilyl group-containing ether-based curing agent can be cured in a short time to produce a uniform rubber-like cured product.

[0118]

[Table 2]

[0119]

[Table 3]

Comparative Reference Example 1 Instead of the hydrosilyl group-containing ether-based curing agent synthesized in Reference Example 1, the following formula was used.

[0121]

Embedded image

A polymethylhydro-dimethylsiloxane copolymer represented by the following formula (average molecular weight: about 2000 to 21)
Reference Example 3 except that a predetermined amount (00: PS 123 manufactured by Chisso Corporation) (the molar ratio of the allyl group in each organic polymer to the hydrosilyl group of PS 123 was 1) was used.
An attempt was made to produce a cured product in the same manner as described above. Each organic polymer containing an allyl group and the polysiloxane have poor compatibility,
It became cloudy during mixing. Some of them were separated when left for a long time. Even after defoaming under reduced pressure, there was a lot of foaming, and a cured product with poor mechanical properties containing a large number of foams was obtained.

Reference Example 4 12.0 g of the allyl ether-terminated polypropylene oxide produced in Synthesis Example 2 and 0.49 g of the hydrosilyl group-containing ether-based curing agent obtained in Reference Example 1 (the molar ratio of allyl group to hydrosilyl group was 1 ) And 14.3 μl of the same chloroplatinic acid catalyst solution used in Reference Example 1 were well stirred and mixed. After the mixture was defoamed by centrifugation, it was poured into a mold having a length of 6 cm, a width of 0.8 cm and a depth of 1.8 cm. 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. When the hardness was measured by a hardness measurement method specified in JIS K 6301 5-2 Spring type hardness test (A type), the surface of the cured product was 22 and the back surface was 21, and a sample having good deep curability was obtained. Was.

Reference Example 5 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, cyclic hydrogen polysiloxane

[0125]

Embedded image

(LS860 manufactured by Shin-Etsu Chemical Co., Ltd.)
0) 29.73 g (124 mmol) was charged into the flask. Isophthalic acid diallyl ester (manufactured by Wako Pure Chemical Industries, Ltd.) 9.84 g (40 mmol) and chloroplatinic acid catalyst solvent solution _{H 2 PtCl 6 · 6H 2 O} 1.0g ethanol / 1,2-dimethoxyethane (1 / 9 V /
V) dissolved in 9 g) 82 μl of toluene 100 m
1 and mixed well, then charged into a dropping funnel. The flask was heated to 65-70 ° C and the toluene solution was added dropwise over 100 minutes. Further, when an IR spectrum was taken at the time when the reaction was performed for 1 hour, 1640 cm
^Since the absorption derived from the olefin of ^-1 had completely disappeared, the reaction was terminated at this point. 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. This viscous liquid is 300 MHz ¹ H
-Identification by NMR, IR spectrum, and the like revealed that the compound was a Si-H group-containing ester-based curing agent having the following structural formula.

[0127]

Embedded image

By comparing the calculated intensity ratio with the proton intensity ratio (actually measured value: 0.220) of Si—H and Si—CH _{3 in the} 300 MHz ¹ H-NMR spectrum, when n = 1: 8 /36=0.222 When n = 2: 10/48 = 0.208 The curing agent had an average of n = 1 (MW = 1214) of 86.
%, N = 2 (MW = 1701) was a mixture consisting of 14%. Based on this, the number of Si—H groups in the unit weight was calculated to be 0.649 mol / 100 g.

IR analysis (neat, cm ^-1 ): 3050
(W), 2940 (S), 2910 (S), 2150
(S, ν _Si-H ), 1720 (S, ν _{C = O} ), 1605
(M), 1300 (S), 1255 (S), 1070
(Bs, ν _SiOSi ) ¹ H-NMR analysis (300 MHz): See FIG. 3

Reference Example 6 In order to examine the compatibility between the Si—H group-containing ester-based curing agent synthesized in Reference Example 5 and various allyl group-containing organic polymers having a main chain skeleton, as shown in Table 4, In combination, the predetermined amount of the curing agent and the organic polymer 1.30 produced in Synthesis Examples 2 to 6 were used.
g was mixed well, and after defoaming by centrifugation, the mixed state was observed. Some were slightly cloudy, but generally transparent and uniform. It was found that the Si-H group-containing ester-based curing agent had good compatibility with various organic polymers.

Next, in order to examine the curability, a predetermined amount of a 10-fold diluted solution of the chloroplatinic acid catalyst solution used in Reference Example 5 was added to each of the above mixtures and mixed well. A part of the mixture is placed on a gelation tester (manufactured by Nissin Kagaku Co., Ltd.),
At a predetermined temperature, a snap-up time (time until the rubber elasticity is developed) was measured. The results are shown in Table 4, and it was found that the composition was quick-curing at high temperatures.

[0132]

[Table 4]

REFERENCE EXAMPLE 7 A predetermined amount of the Si-H group-containing ester-based curing agent synthesized in Reference Example 5, 8.32 g of various allyl group-containing polymers produced in Synthesis Examples 2 to 6, and used in Reference Example 5 The chloroplatinic acid catalyst solution was mixed well at the ratio shown in Table 5. 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 80 ° C. for 1 hour to obtain a uniform rubbery cured product having a thickness of about 3 mm. JIS K from the sheet of the cured product
No. 3 dumbbell according to 6301, punching speed 2
A tensile test was performed at 00 mm / min. Table 5 shows the results.

It was found that the use of the above-mentioned ester-based curing agent containing a hydrosilyl group can be cured in a short time to produce a uniform rubber-like cured product.

[0135]

[Table 5]

Comparative Reference Example 2 In place of the hydrosilyl group-containing ester-based curing agent synthesized in Reference Example 5, a compound represented by the following formula:

[0137]

Embedded image

A polymethylhydro-dimethylsiloxane copolymer represented by the following formula (average molecular weight: about 2000 to 21)
Reference Example 7 except that a predetermined amount (00: PS 123 manufactured by Chisso Corp.) (the molar ratio of the allyl group in each organic polymer to the hydrosilyl group of PS 123 was 1) was used.
An attempt was made to produce a cured product in the same manner as described above. Each organic polymer containing an allyl group and the polysiloxane have poor compatibility,
It became cloudy during mixing. Some of them were separated when left for a long time. Even after defoaming under reduced pressure, there was a lot of foaming, and a cured product with poor mechanical properties containing a large number of foams was obtained.

Reference Example 8 12.0 g of the allyl ether-terminated polypropylene oxide produced in Synthesis Example 2 and 0.46 g of the hydrosilyl group-containing ester curing agent obtained in Reference Example 5 (the molar ratio of allyl group to hydrosilyl group was 1 ) And 8 μl of the same chloroplatinic acid catalyst solution used in Reference Example 5 were mixed well by stirring. After the mixture was defoamed by centrifugation, the length was 6 cm and the width was 0.8 c.
m and a depth of 1.8 cm. 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
K6301 5-2 Term Spring Type Hardness Test (A
When the hardness was measured by the hardness measurement method specified in (Form), the surface of the cured product was 20 and the back was 19, and a sample having good deep curability was obtained.

REFERENCE EXAMPLE 9 A 200 ml four-necked flask was equipped with a cooling tube equipped with a three-way cock, a pressure equalizing dropping funnel, a thermometer, a magnetic chip,
One with a glass stopper attached was prepared. Cyclic polyhydrogensiloxane under nitrogen atmosphere:

[0141]

Embedded image

(LS860 manufactured by Shin-Etsu Chemical Co., Ltd.)
0) 12.03 g (50 mmol) and toluene 20
ml was charged into the flask. 1,9-decadiene 2.
76 g (20 mmol) of a chloroplatinic acid catalyst solution (H ₂ P
tCl ₆ · 6H ₂ O 1g ethanol 1 g, 1,2-solution was dissolved in dimethoxyethane 9 g) were charged 20μl into the dropping funnel which was dissolved in toluene 30 ml. The flask was placed in a 50 ° C. oil bath, and the toluene solution was dropped into the flask over 2 hours under a nitrogen atmosphere. At the time of further reacted for 1 hour After completion of the dropwise addition 50 ° C., was measured for IR spectrum, 1640 cm ^-1
Since the absorption of the olefin near was completely lost,
At this point, the reaction was terminated. The toluene solution after the completion of the reaction was added to a saturated aqueous solution of ammonium chloride (100 ml ×
2) After washing with exchanged water (100 ml × 1), Na ₂ SO ₄
And dried. Na ₂ SO ₄ was removed by filtration, volatiles were removed by evaporation, and the mixture was degassed under reduced pressure at 80 ° C. to obtain 9.11 g of a colorless transparent liquid. The hydrosilyl group in the hydrocarbon-based curing agent was confirmed as a strong absorption at 2170 cm ^-1 . In addition, 300 MHz NMR analysis
curing agent by comparing i-H proton intensity ratio between the peak and the Si-CH ₃ and (actually measured value 0.216) and the intensity ratio of the calculated has the following structure formula average [n = 1 (MW = 998) is 53%, and n = 2 (MW = 1)
377) was a 47%] mixture. If the number of Si-H groups in a unit weight is calculated based on this, it is 0.1.
It was 769 mol / 100 g.

[0143]

Embedded image

Reference Example 10 The compatibility of the Si—H group-containing hydrocarbon curing agent produced in Reference Example 9 with various kinds of allyl group-containing organic polymers having a main chain skeleton is shown in Table 6. In a suitable combination, a predetermined amount of the curing agent and 1.0 g of the organic polymer were mixed well, and after centrifugal defoaming, the mixed state was observed. Some were slightly cloudy, but generally transparent and uniform. It was found that the Si-H-containing hydrocarbon-based curing agent had good compatibility with various organic polymers.

Next, in order to examine the curability, a predetermined amount of a 10-fold diluted solution of the chloroplatinic acid catalyst solution used in Reference Example 9 was added to each of the above-mentioned mixtures and mixed well. A part of the mixture is placed on a gelation tester (manufactured by Nissin Kagaku Co., Ltd.),
The snap-up time (time until rubber elasticity) was measured at 100 ° C. The results are shown in Table 6, and it was found that the composition was quick-curing at high temperatures.

[0146]

[Table 6]

REFERENCE EXAMPLE 11 Predetermined amounts of the Si—H group-containing hydrocarbon-based curing agent produced in Reference Example 9, prescribed amounts of various allyl group-containing polymers produced in Synthesis Examples 2 and 4, and The chloroplatinic acid catalyst solution was mixed well at the ratio shown in Table 7. 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 about 3 mm. JIS from the sheet of the cured product
A No. 3 dumbbell compliant with K6301 was punched out and subjected to a tensile test at a tensile speed of 200 mm / min. Table 7 shows the results
Shown in

From Table 7, it was found that the composition using the above-mentioned hydrosilyl group-containing hydrocarbon-based curing agent can be cured in a short time to produce a uniform rubber-like cured product.

[0149]

[Table 7]

Comparative Reference Example 3 Instead of the hydrosilyl group-containing hydrocarbon-based curing agent synthesized in Reference Example 9, the following formula:

[0151]

Embedded image

A polymethylhydro-dimethylsiloxane copolymer represented by the following formula (average molecular weight: about 2000 to 21)
Reference Example 1 except that a predetermined amount (00: PS 123 manufactured by Chisso Corporation) (the molar ratio of the allyl group in each organic polymer to the hydrosilyl group of PS 123 was 1) was used.
An attempt was made to produce a cured product in the same manner as in 1. Each of the organic polymers having an allyl group and the polysiloxane had poor compatibility and became turbid during mixing. Some of them were separated when left for a long time. Even after defoaming under reduced pressure, there was a lot of foaming, and a cured product with poor mechanical properties containing a large number of foams was obtained.

Reference Example 12 10.0 g of the allyl ether-terminated polypropylene oxide produced in Synthesis Example 2 and 0.30 g of the hydrosilyl group-containing hydrocarbon curing agent obtained in Reference Example 9 (the molar ratio of allyl group to hydrosilyl group was 10 μl of the same chloroplatinic acid catalyst solution used in 1) and Reference Example 9 was mixed well with stirring.
The mixture was poured into a polyethylene test tube having a diameter of about 1.5 cm and a length of about 10 cm, subjected to centrifugation and degassing at room temperature under reduced pressure, and then cured at 80 ° C. for 1 hour. After the curing, the bottom of the polyethylene test tube was cut and the cut surface was observed.

REFERENCE EXAMPLE 13 A 200 ml four-necked flask was equipped with a three-way cocked cooling tube, a pressure-equalizing dropping funnel, a thermometer, a magnetic chip,
One with a glass stopper attached was prepared. Cyclic polyhydrogensiloxane under nitrogen atmosphere

[0155]

Embedded image

(LS860 manufactured by Shin-Etsu Chemical Co., Ltd.)
0) 12.03 g (50 mmol) and toluene 20
ml was charged into the flask. Diethylene glycol diallyl carbonate:

[0157]

Embedded image

(RAV-7N, manufactured by Mitsui Petrochemical Co., Ltd.)
5.49 g (20 mmol) of a chloroplatinic acid catalyst solution (H
The ₂ PtCl ₆ · 6H ₂ O 1g ethanol 1 g, 1, 2
A solution prepared by dissolving 41 μl of a solution dissolved in 9 g of dimethoxyethane 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 nitrogen atmosphere. When the IR spectrum was measured after completion of the dropwise addition, the olefin absorption near 1640 cm ^-1 had completely disappeared, and the reaction was terminated at this point. The reaction mixture was evaporated to remove volatiles, yielding 10.2 g of a slightly viscous pale yellow light liquid. The hydrosilyl group of the carbonate compound is 217 in the IR spectrum.
A strong absorption of 0 cm ^-1 was confirmed. Also 300MH
By comparing the peak intensity of Si—H with the proton intensity of Si—CH ₃ (actually measured value: 0.181) and the calculated intensity ratio by NMR analysis of z, the curing agent is averaged by the following formula: It was found to have the following structure. Based on this, the number of Si—H groups in the unit weight is calculated to be 0.47 mol / 1.
00 g.

[0159]

Embedded image

Reference Example 14 In order to examine the compatibility between the Si—H group-containing carbonate-based compound produced in Reference Example 13 and various kinds of allyl group-containing organic polymers having a main chain skeleton, combinations shown in Table 8 were used. so,
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 Si-H
It was found that the group-containing compound had good compatibility with various organic polymers.

Next, in order to examine the curability, a predetermined amount of a 10-fold diluted solution of the chloroplatinic acid catalyst solution used in Reference Example 13 was added to each of the above mixtures and mixed well. A part of the mixture is taken on a gelling tester (manufactured by Nissin Chemical Co., Ltd.),
At 80 ° C., a snap-up time (time until rubber elasticity) was measured. The results are shown in Table 8, and it was found that the composition was quick-curing at high temperature.

[0162]

[Table 8]

Reference Example 15 A predetermined amount of the Si—H group-containing carbonate compound produced in Reference Example 13, 10 g of various allyl group-containing polymers produced in Synthesis Examples 2 to 4, and chloroplatinic acid used in Reference Example 13 The catalyst solution was mixed well at the ratio shown in Table 9. 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 80 ° C. for 1 hour to obtain a uniform rubbery cured product having a thickness of about 3 mm. JIS from the sheet of the cured product
A No. 3 dumbbell compliant with K6301 was punched out and subjected to a tensile test at a tensile speed of 200 mm / min. Table 1 shows the results
0 is shown.

From Table 10, it was found that the use of the above-mentioned carbonate compound containing a hydrosilyl group can be cured in a short time to produce a uniform rubber-like cured product.

[0165]

[Table 9]

[0166]

[Table 10]

Comparative Reference Example 4 Instead of the hydrosilyl group-containing carbonate compound synthesized in Reference Example 13, a compound represented by the following formula:

[0168]

Embedded image

A polymethylhydro-dimethylsiloxane copolymer represented by the following formula (average molecular weight: about 2000 to 21)
Reference Example 1 except that a predetermined amount (00: PS 123 manufactured by Chisso Corporation) (the molar ratio of the allyl group in each organic polymer to the hydrosilyl group of PS 123 was 1) was used.
Production of a cured product was attempted in the same manner as in Example 5. Each of the organic polymers having an allyl group and the polysiloxane had poor compatibility and became turbid during mixing. Some of them were separated when left for a long time. Even after defoaming under reduced pressure, there was a lot of foaming, and a cured product with poor mechanical properties containing a large number of foams was obtained.

Reference Example 16 10 g of allyl ether-terminated polypropylene oxide produced in Synthesis Example 2, 0.5 g of the hydrosilyl group-containing carbonate compound obtained in Reference Example 13 (molar ratio of allyl group to hydrosilyl group is 1) and Reference 12 μl of the same chloroplatinic acid catalyst solution used in Example 13 was mixed well with stirring. The mixture was poured into a polyethylene test tube having a diameter of about 1.5 cm and a length of about 10 cm, subjected to centrifugation and degassing at room temperature under reduced pressure, and then cured at 80 ° C. for 1 hour. After the curing, the bottom of the polyethylene test tube was cut and the cut surface was observed.

[0171]

The composition containing the curing agent of the present invention can provide a uniform cured product having good mechanical properties, rapid curability, and excellent deep curability.

[Brief description of the drawings]

FIG. 1 is a 300 MHz ¹ H-NMR spectrum of the diallyl ether of bisphenol A obtained in Synthesis Example 1.

FIG. 2 is a 300 MHz ¹ H-NMR spectrum of the Si-H group-containing ether-based curing agent obtained in Reference Example 1.

FIG. 3 is a 300 MHz ¹ H-NMR spectrum of the Si—H group-containing ester-based curing agent obtained in Reference Example 5.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 81/04 C08L 101/02 101/02 C08K 5/54 (31) Priority claim number Japanese Patent Application No. 1-139940 (32) Priority Date June 1, 2001 (June 6.1, 1989) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 1-145672 (32) Priority date June 7, 2001 Date (1989.6.7) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 1-145673 (32) Priority date June 7, 2001 (1989.6.7) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 1-145674 (32) Priority date June 7, 2001 (1989.6.7) (33) Priority claim Country Japan (JP) (31) Priority claim number Japanese Patent Application No. 1-153143 (32) Priority date June 15, 1999 (1989.6.15) (33) Priority claim country Japan (JP) Preface (72) Inventor Kazuya Yonezawa 1-2-80 Yoshida-cho, Hyogo-ku, Kobe City, Hyogo Prefecture Inside the Central Research Laboratory of Kanegafuchi Chemical Industry Co., Ltd. (56) References JP-A-61-254625 (JP, A) (58) Surveyed fields (Int.Cl. ⁷ , DB name) C08L 83/04 C08L 83/05 C08L 83/07 C08K 5/541 C08L 25/04 C08L 67/02 C08L 77/00 C08L 81/04 C08L 101/02

Claims (23)

(57) [Claims] 1. A compound of the general formula (IX): Wherein R ⁵ is a hydrocarbon group having 1 to 50 carbon atoms and R ⁸ is a hydrogen atom or a methyl group. (A3)
And a polyvalent hydrogen silicon compound (B) in the presence of a hydrosilylation catalyst, and a hydrosilyl group-containing alkenyl group-containing organic polymer curing agent produced so that the hydrosilyl group remains even after the reaction. Wherein the polyvalent hydrogen silicon compound (B) is (CH ₃ ) ₂ SiH ₂ , (C ₆ H ₅ ) ₂ SiH ₂ ,
CH ₃ SiH ₃ , C ₆ H ₅ SiH ₃ , (C ₂ H ₅ ) ₂ SiH ₂ ,
A monosilane compound represented by CH ₃ (CH ₂ ) ₅ SiH ₃ ; A polysilicon compound represented by the formula: Embedded image Embedded image Wherein the alkenyl group-containing organic polymer is a polyester-based polymer, an acrylate ester, Polymer, acrylic acid ester copolymer, hydrocarbon polymer, polycarbonate polymer, polysulfide polymer, polyamide polymer, diallyl phthalate polymer at least one molecule in the molecule selected from the group consisting of organic polymer der containing pieces of alkenyl group is, the cured product is light
Organic curing agent that Do the cured product other than academic for crosslinked siloxane polymers. 2. The polyvalent hydrogen silicon compound as the component (B) is represented by the following formula: Embedded image Embedded image The organic curing agent according to claim 1, which is at least one kind of a compound selected from the group consisting of linear, branched, and cyclic polyvalent hydrogen polysiloxanes represented by the formula: 3. The polyvalent hydrogen silicon compound as the component (B) is represented by the following formula: The organic curing agent according to claim 1, which is at least one compound selected from the group consisting of: 4. The polyvalent hydrogen silicon compound as the component (B) is represented by the following formula: The organic curing agent according to claim 1, which is at least one compound selected from the group consisting of: 5. A compound (A) represented by the general formula (IX)
3) R ⁵ in the [of 11] A monovalent group selected from the group consisting of:
5. The organic curing agent according to 3 or 4. 6. A compound (A3) represented by the general formula (IX) according to claim 1 is reacted with the polyvalent hydrogen silicon compound (B) according to claim 1 in the presence of a hydrosilylation catalyst. The method for producing an organic curing agent according to claim 1, further comprising a hydrosilyl group produced so that the hydrosilyl group remains. 7. The method according to claim 6, wherein the component (B) is the compound described in claim 2. 8. The method according to claim 6, wherein the component (B) is the compound described in claim 3. 9. The method according to claim 6, wherein the component (B) is the compound described in claim 4. 10. An optical frame comprising the following components (C), (D) and (E) as essential components:
A curable composition that becomes a cured product other than the bridged siloxane polymer . (C) the organic curing agent according to claim 1, 2, 3, 4, or 5, (D) a polyester-based polymer, an acrylate-based polymer, an acrylate-based copolymer, a hydrocarbon-based polymer, (E) a hydrosilylation catalyst, an organic polymer containing at least one alkenyl group in a molecule selected from the group consisting of a polycarbonate polymer, a polysulfide polymer, a polyamide polymer, and a diallyl phthalate polymer. 11. The curable composition according to claim 10, wherein the component (C) is the organic curing agent according to claim 1. 12. The curable composition according to claim 10, wherein the molar ratio of the hydrosilyl group to the alkenyl group of the component (C) and the component (D) is 0.2 to 5.0. 13. The curable composition according to claim 10, wherein the component (C) is the organic curing agent according to claim 2. 14. The curable composition according to claim 10, wherein the component (C) is the organic curing agent according to claim 3. 15. The curable composition according to claim 10, wherein the component (C) is the organic curing agent according to claim 4. 16. The organic polymer (D) having a molecular weight of 5
10. The composition of claim 10, 11, 12, 1, or 100.
16. The curable composition according to 3, 14, or 15. 17. The method according to claim 10, wherein the alkenyl group of the organic polymer as the component (D) is present at a molecular terminal.
17. The curable composition according to 3, 14, 15 or 16. 18. The organic polymer as the component (D) is selected from the group consisting of a polyester polymer, an acrylate polymer, an acrylate copolymer, a hydrocarbon polymer, and a polycarbonate polymer. The curable composition according to claim 10, 11, 12, 13, 14, 15, 16, or 17, which is a prepared organic polymer. 19. The component (C) is the organic curing agent according to claim 5, and the organic polymer (D) is a hydrocarbon polymer. 14,
19. The curable composition according to 15, 16, 17 or 18. 20. The curable composition according to claim 19, wherein the organic polymer as the component (D) is a saturated hydrocarbon polymer. 21. The organic polymer as the component (D) is obtained by hydrogenating an ethylene-propylene copolymer, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, isoprene, or a copolymer of butadiene with acrylonitrile or styrene. 21. The curable composition according to claim 20, which is a polyolefin-based polymer obtained. 22. An acrylate polymer and / or an acrylate copolymer obtained by using a vinyl monomer having an alkenyl group as a copolymerizable monomer as the component (D) organic polymer. Claims 10, 11, 12, 13, 14, 15, 1
19. The curable composition according to 6, 17, or 18. 23. A functional group and an alkenyl group capable of reacting with a hydroxyl group in an acrylate polymer and / or acrylate copolymer in which the organic polymer (D) has a hydroxyl group at a terminal or a side chain. 19. The curable composition according to claim 10, which is a polymer obtained by reacting a compound having the following.