JP2001342350A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which has improved workability by reducing a viscosity increased when an inorganic filler is added to the curable composition. SOLUTION: The curable composition comprises four components, i.e., (I) a vinyl polymer containing at least one alkenyl group which enables hydrosilylation reaction in the molecule, (II) a hydrosilyl group-containing compound, (III) at least one organometallic compound to be selected from the group consisting of an organoaluminum compound, an organo-titanium compound, and an organotin compound, and (IV) an inorganic filler as the essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a curable composition. More specifically, the present invention relates to a curable composition containing an alkenyl group-containing vinyl polymer and a hydrosilyl group-containing compound.

[0002]

2. Description of the Related Art JP-A-9-272714 discloses a method of obtaining a curable composition by crosslinking a alkenyl group-containing vinyl polymer with a hydrosilyl group-containing compound. However, this curable composition has a relatively high viscosity, so that it may be necessary to reduce the viscosity of the resin component in order to mix various additives and fillers.

[0003]

An object of the present invention is to provide a vinyl polymer having excellent oil resistance, heat resistance, weather resistance and the like,
In the curable composition which can be cured by the hydrosilylation reaction, the viscosity of the curable composition is to be reduced in order to improve workability such as facilitating the blending of various additives and fillers.

[0004]

Means for Solving the Problems When the present inventors apply a alkenyl group-containing vinyl polymer to a curing system (addition-type curing system) which can be cured by a hydrosilylation reaction, the present invention relates to an organoaluminum compound and / or an organoaluminum compound. Organic titanium compounds and / or
Alternatively, it has been found that by adding an organic tin compound, a curable composition whose viscosity has been significantly reduced can be obtained. That is, the present invention provides the following four components: a vinyl polymer (I) having at least one alkenyl group capable of hydrosilylation reaction in a molecule; a hydrosilyl group-containing compound (II); and an organic aluminum compound, an organic titanium compound, and an organic compound. It is a curable composition comprising at least one organometallic compound (III) selected from the group consisting of tin compounds and an inorganic filler (IV) as an essential component. Hereinafter, the present invention will be described in detail.

<< Regarding Vinyl Polymer (I) >><MainChain> The vinyl monomer constituting the main chain of the vinyl polymer (I) of the present invention is not particularly limited, and various types are used. be able to. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, -n (meth) acrylate
-Butyl, isobutyl (meth) acrylate, -tert-butyl (meth) acrylate, -n- (meth) acrylate
-Pentyl, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid-
n-heptyl, n-octyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, (meth)
Dodecyl acrylate, phenyl (meth) acrylate,
Toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) Acrylic acid-2
-Hydroxypropyl, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, an ethylene oxide adduct of (meth) acrylic acid, Trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutyl (meth) acrylate Ethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate 2- (fluoro) (meth) acrylate Shiruechiru, (meth) acrylate, 2-perfluoro decyl ethyl, (meth) acrylic acid 2
(Meth) acrylic acid monomers such as perfluorohexadecylethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, and fluorine. Fluorine-containing vinyl monomers such as vinylidene fluoride; vinyltrimethoxysilane,
Silicon-containing vinyl monomers such as vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid,
Monoalkyl esters and dialkyl esters of fumaric acid; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile, methacrylic acid Vinyl monomers containing nitrile groups such as lonitrile; vinyl monomers containing amide groups such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate,
Vinyl esters such as vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride;
Allyl alcohol and the like can be mentioned. These may be used alone or a plurality of them may be copolymerized. Among them, styrene-based monomers and (meth) acrylic-acid-based monomers are preferred from the viewpoint of the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, particularly preferred are acrylate monomers, and still more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers, or further, may be subjected to block copolymerization. In such a case, it is preferable that these preferable monomers are contained in a weight ratio of 40%. In the above expression format, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

The molecular weight distribution of the vinyl polymer (I) of the present invention, that is, the ratio (Mw) between the weight average molecular weight and the number average molecular weight measured by gel permeation chromatography.
/ Mn) is not particularly limited, but is preferably less than 1.8, preferably 1.7 or less, more preferably 1.6 or less, further preferably 1.5 or less, and particularly preferably. Is 1.4 or less, and most preferably 1.3 or less. In the GPC measurement in the present invention,
Usually, chloroform is used as a mobile phase, the measurement is carried out using a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene. The number average molecular weight of the vinyl polymer (I) of the present invention is not particularly limited.
The range is preferably from 0 to 1,000,000,
100,000 is more preferred. When the molecular weight is too low, the intrinsic properties of the vinyl polymer are hardly exhibited, and when it is too high, handling becomes difficult.

<Synthesis Method of Polymer> The vinyl polymer (I) of the present invention can be obtained by various polymerization methods, and the method is not particularly limited. Therefore, the radical polymerization method is preferred. Among radical polymerizations, controlled radical polymerization is preferred, living radical polymerization is more preferred, and atom transfer radical polymerization is particularly preferred. The method of introducing an alkenyl group is a method of directly introducing an alkenyl group in a polymerization reaction system, synthesizing a vinyl polymer having a specific functional group, and converting the specific functional group to an alkenyl group in one or several steps of reaction. There is a conversion method. Hereinafter, these synthesis methods will be described in detail.

[0008]Radical polymerization  Of vinyl polymer having functional group by radical polymerization method
The synthesis methods are “general radical polymerization method” and “controlled radio
Polymerization method ”. "General radical polymerization method"
Refers to the use of polymerization initiators such as azo compounds and peroxides.
Vinyl monomer having a certain functional group (hereinafter referred to as “functionality
Monomers. " ) And other vinyl monomers
This is a method of copolymerizing. On the other hand, "controlled radical polymerization
`` Method '' is to introduce a specific functional group at a controlled position such as the terminal.
It is a method that can be entered.

[0009]General radical polymerization  “General radical polymerization method” is a simple method.
It can be used for
And the specific functional group is introduced into the polymer only stochastically
Absent. Therefore, when obtaining a polymer having a high functionalization rate,
Need to use a large amount of functional monomer,
Use of the above-mentioned polymer in which the specific functional group is not introduced
However, there is a problem that the combination becomes large. Free radio deer
Polymer with high molecular weight distribution and high viscosity
There is also a problem that it can only be obtained.

[0010]Controlled radical polymerization  “Controlled radical polymerization method” includes “chain transfer agent method” and “Livin”
A radical polymerization method ”. "control
The radical polymerization method uses a chain transfer agent with a specific functional group.
Characterized by conducting polymerization using a functional group at the terminal
A vinyl polymer is obtained. On the other hand, "Living radio
The polymer polymerization method uses a special polymerization system to produce polymer.
Long terminals can grow without causing side reactions such as termination reactions.
And features. As a result, "Living radical polymerization"
In the “method”, a polymer having a molecular weight almost as designed is obtained.

[0011]Chain transfer agent method  "Chain transfer agent method" is compared with "general radical polymerization method"
It is possible to introduce functional groups into polymer terminals relatively quantitatively
Because it can be used, it can be used in the present invention. But,
Chains with a significant amount of specific functional groups for the initiator
Transfer agent is required, including processing such as recovery of chain transfer agent
And there is an economic problem. In addition, the above "general radical
As in the case of the polymerization method, the molecular weight is
The problem of wide distribution and high viscosity
There is also. Radical polymerization using chain transfer agent (telomer)
Is not particularly limited, but a terminal structure suitable for the present invention.
A method for obtaining a vinyl polymer having a structure is as follows.
Two methods are illustrated. JP-A-4-132706
A halogenated hydrocarbon as shown in
Method for obtaining a halogen-terminated polymer by using as
Japanese Patent Publication No. 61-271306, Japanese Patent No. 2594402
As disclosed in Japanese Unexamined Patent Application Publication No. 54-47782
Hydroxyl-containing mercaptan or hydroxyl-containing polysulfur
Hydroxyl-terminated polymer using sulfide etc. as chain transfer agent
Is a way to get

[0012]Living radical polymerization  Radical polymerization has a high polymerization rate and radical
Generally, termination reaction due to ring etc. is likely to occur
Is said to be difficult to control. However, "Living
The radical polymerization method differs from the polymerization method described above in that the radical polymerization method
Although it is polymerization, it is difficult for side reactions such as termination reaction to occur.
Narrow distribution of molecular weight (Mw / Mn is about 1.1 to 1.5)
As a result, coalescing is obtained and the charge ratio of monomer and initiator
Can control molecular weight freely
It has the feature of. Therefore, "Living radical polymerization"
The method is to obtain a polymer with narrow molecular weight distribution and low viscosity.
And polymerize monomers with specific functional groups
Can be introduced almost anywhere in the body,
As a method for producing a vinyl polymer having a specific functional group
Is more preferred. Note that living polymerization is narrow.
In a sense, the terminus is always active and a molecular chain is formed.
This refers to a prolonged polymerization.
The activated and activated ones are in equilibrium
Pseudo-living polymerization, which grows in a manner, is also included. In the present invention
The latter definition is also the latter.

The "living radical polymerization method" has been actively studied by various groups in recent years. Examples include the Journal of American Chemical Society (J. Am. Chem. Soc.),
994, vol. 116, p. 7943, using a cobalt porphyrin complex, Macromolecules, 1994;
Vol. 27, p. 7228, which uses a radical scavenger such as a nitroxide compound, and "atom transfer radical polymerization" using an organic halide or the like as an initiator and a transition metal complex as a catalyst (Atom Transfer Rad)
ical Polymerization: ATRP)
And so on. Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which a vinyl monomer is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned "living radical polymerization method". In addition to the features described above, the production of vinyl polymers having specific functional groups is possible because of having a halogen or the like at the terminal that is relatively advantageous for the functional group conversion reaction and having a high degree of freedom in designing initiators and catalysts. The method is more preferable. As this atom transfer radical polymerization method, for example, M
atyjaszewski, et al., Journal of American Chemical Society (J. Am. Chem.
Soc. 1995, 117, 5614, Macromolecules 19
1995, Vol. 28, p. 7901, Science
ce) 1996, vol. 272, p. 866, WO 96/3
No. 0421, WO97 / 18247, WO9
8/01480, WO98 / 40415,
Or Sawamoto et al., Macromolecules 1995, 28
Volume, page 1721, JP-A-9-208616, JP-A-8-41117, and the like.

The atom transfer radical polymerization of the present invention includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization refers to a highly oxidized state when a normal atom transfer radical polymerization catalyst generates radicals, for example, Cu (II ′) when Cu (I) is used as a catalyst.
Is reacted with a general radical initiator such as peroxide to produce an equilibrium state similar to that of atom transfer radical polymerization (Macromolecule).
es 1999, 32, 2872). In the present invention, there is no particular limitation on which of these living radical polymerization methods to use, but an atom transfer radical polymerization method is preferred. Hereinafter, living radical polymerization will be described.

First, a method using a radical scavenger such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= N
-O.) Is used as a radical capping agent. Such compounds include, but are not limited to, 2, 2,
6,6-substituted-1-piperidinyloxy radicals and 2,
Preferred are nitroxy free radicals from cyclic hydroxyamines, such as 2,5,5-substituted-1-pyrrolidinyloxy radicals. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group and an ethyl group is suitable. Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,
2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-
1-pyrrolidinyloxy radical, 1,1,3,3-tetramethyl-2-isoindolinyloxy radical,
N, N-di-t-butylamineoxy radical and the like can be mentioned. Instead of the nitroxy free radical, a stable free radical such as galvinoxyl free radical may be used. The radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator, and the polymerization of the addition-polymerizable monomer proceeds. The combination ratio of both is not particularly limited, but 0.1 to 10 mol of the radical initiator is suitable for 1 mol of the radical capping agent.

As the radical generator, various compounds can be used, but a peroxide capable of generating a radical under polymerization temperature conditions is preferred. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diisopropyl peroxydicarbonate; Peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyoctoate, t-
There are alkyl peresters such as butyl peroxybenzoate. Particularly, benzoyl peroxide is preferred. Further, a radical generator such as a radical-generating azo compound such as azobisisobutyronitrile may be used instead of the peroxide. Macromolecule
As reported in 1995, 28, 2993, instead of using a radical capping agent and a radical generator together, an alkoxyamine compound as shown in the following figure may be used as an initiator.

[0017]

Embedded image

When an alkoxyamine compound is used as an initiator, if the compound has a functional group such as a hydroxyl group as shown in the above figure, a polymer having a functional group at the terminal can be obtained. When this is used in the method of the present invention, a polymer having a functional group at a terminal can be obtained. Polymerization conditions such as a monomer, a solvent, and a polymerization temperature used in the polymerization using the radical scavenger such as the nitroxide compound are not limited, and may be the same as those used for atom transfer radical polymerization described below.

[0019]Atom transfer radical polymerization  Next, more preferable as the living radical polymerization of the present invention.
The atom transfer radical polymerization method will be described. This atom
In transfer radical polymerization, organic halides, especially reactive
Having high carbon-halogen bond content
(For example, a carbonyl compound having a halogen at the α-position
Or a compound having a halogen at the benzyl position), or
Sulfonyl halide compounds are used as initiators
You. To give a concrete example, C₆H₅-CH₂X, C₆H₅-C (H) (X) C
H₃, C₆H₅-C (X) (CH₃)₂  (However, in the above chemical formula, C₆H₅Is a phenyl group, X is
Chlorine, bromine or iodine) R³-C (H) (X) -CO₂R⁴, R³-C (C
H₃) (X) -CO₂R⁴, R³-C (H) (X) -C
(O) R⁴, R³-C (CH₃) (X) -C (O)
R ⁴, Where R³, R⁴Is a hydrogen atom or a group having 1 to 20 carbon atoms
An alkyl group, an aryl group, or an aralkyl group, and X is a salt
Element, bromine or iodine) R³-C₆H₄-SO₂X (In each of the above formulas, R³Is a hydrogen atom or 1 carbon atom
To 20 alkyl groups, aryl groups, or aralkyl
And X is chlorine, bromine, or iodine).

By performing atom transfer radical polymerization of a vinyl monomer using an organic halide or a sulfonyl halide compound as an initiator, a vinyl polymer having a terminal structure represented by the general formula (1) can be obtained. —C (R ¹ ) (R ² ) (X) (1) (wherein, R ¹ and R ² each represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine. Shown.)

As the initiator of the atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having both a functional group that initiates polymerization and a specific functional group that does not initiate polymerization can be used. In such a case, a vinyl polymer having a specific functional group at one main chain terminal and a terminal structure represented by the general formula (1) at the other main chain terminal is obtained. Examples of such a specific functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, and an amide group.

The organic halide having an alkenyl group is not limited, and examples thereof include those having a structure represented by the general formula (2). R ⁶ R ⁷ C (X) -R ⁸ -R ⁹ -C (R ⁵ ) = CH ₂ (2) (wherein, R ⁵ is hydrogen or a methyl group, and R ⁶ and R ⁷ are hydrogen or carbon A monovalent alkyl group, an aryl group, or an aralkyl represented by the following formulas 1 to 20, or ones linked to each other at the other end, R ⁸ represents —C (O) O— (ester group), Keto group), or o-, m-, p
A phenylene group, R ⁹ is a direct bond, or has 1 to 2 carbon atoms;
X is a divalent organic group of 0 and may contain one or more ether bonds. X is chlorine, bromine, or iodine. Specific examples of the substituents R ⁶ and R ⁷ include hydrogen, a methyl group,
Examples include an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. R ⁶ and R
⁷ may be linked at the other end to form a cyclic skeleton.

Specific examples of the organic halide having an alkenyl group represented by the general formula (2) include XCH ₂ C (O) O (CH ₂ ) _n CH ＝ CH ₂ , H ₃ CC (H) (X ) C (O) O (CH ₂ ) _n CH = C
H ₂ , (H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n CH = C
H ₂ , CH ₃ CH ₂ C (H) (X) C (O) O (CH ₂ ) _n C
H = CH ₂ ,

[0024]

Embedded image

(In each of the above formulas, X represents chlorine, bromine,
Or iodine, n is an integer of 0 to 20) XCH₂C (O) O (CH₂)_nO (CH₂)_mCH =
CH₂, H₃CC (H) (X) C (O) O (CH₂)_nO (CH
₂)_mCH = CH₂, (H₃C)₂C (X) C (O) O (CH₂)_nO (CH
₂)_mCH = CH₂, CH₃CH₂C (H) (X) C (O) O (CH₂)_nO
(CH₂)_mCH = CH ₂,

[0026]

Embedded image

(In each of the above formulas, X represents chlorine, bromine,
Or iodine, n is an integer of 1 to 20, m is an integer of 0 to 20
Number) o, m, p-XCH₂-C₆H₄− (CH₂)_n-CH
= CH₂, O, m, p-CH₃C (H) (X) -C₆H₄− (CH
₂)_n-CH = CH₂, O, m, p-CH₃CH₂C (H) (X) -C₆H₄−
(CH₂)_n-CH = CH₂(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH₂-C₆H₄− (CH₂)_n-O-
(CH₂)_m-CH = CH₂, O, m, p-CH₃C (H) (X) -C₆H₄− (CH
₂)_n-O- (CH₂) _m-CH = CH₂, O, m, p-CH₃CH₂C (H) (X) -C₆H₄−
(CH₂)_n-O- (CH₂)_mCH = CH₂(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH₂-C₆H₄-O- (CH₂)_n−
CH = CH₂, O, m, p-CH₃C (H) (X) -C₆H₄-O-
(CH₂)_n-CH = CH ₂, O, m, p-CH₃CH₂C (H) (X) -C₆H₄−
O- (CH₂)_n-CH = CH₂(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH₂-C₆H₄-O- (CH₂)_n−
O- (CH₂)_m-CH = CH₂, O, m, p-CH₃C (H) (X) -C₆H₄-O-
(CH₂)_n-O- (CH ₂)_m-CH = CH₂, O, m, p-CH₃CH₂C (H) (X) -C₆H₄−
O- (CH₂)_n-O- (CH₂)_m-CH = CH₂(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20)

The organic halide having an alkenyl group further includes a compound represented by the general formula (3). _{^{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (3) ( ^{wherein, R 5, R 6, R} 7, R 9, X in the above Same, R
¹⁰ is a direct bond, -C (O) O- (ester group),-
C (O) - (keto group), or, o-, m-, p-phenylene represents a group) ^{R 8} is a direct bond or a divalent organic group (one or more ether bonds having 1 to 20 carbon atoms May be included), but in the case of a direct bond, a vinyl group is bonded to the carbon to which the halogen is bonded, and the compound is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, C (O) is used as R ^10.
It is not always necessary to have an O group, a phenylene group or the like, and a direct bond may be used. When R ⁹ is not a direct bond,
In order to activate the carbon-halogen bond, R ¹⁰ is preferably a C (O) O group, a C (O) group, or a phenylene group.

The compound of the general formula (3) is specifically exemplified.
Then CH₂= CHCH₂X, CH₂= C (CH₃)
CH₂X, CH₂= CHC (H) (X) CH₃, CH₂= C (CH
₃) C (H) (X) CH ₃, CH₂= CHC (X) (CH₃)₂, CH₂= CHC
(H) (X) C₂H₅, CH₂= CHC (H) (X) CH (CH₃)₂, CH₂= CHC (H) (X) C₆H₅, CH₂= CHC
(H) (X) CH₂C₆H₅, CH₂= CHCH₂C (H) (X) -CO₂R, CH₂= CH (CH₂)₂C (H) (X) -CO₂R, CH₂= CH (CH₂)₃C (H) (X) -CO₂R, CH₂= CH (CH₂)₈C (H) (X) -CO₂R, CH₂= CHCH₂C (H) (X) -C₆H₅, CH₂= CH (CH₂)₂C (H) (X) -C₆H₅, CH₂= CH (CH₂)₃C (H) (X) -C₆H₅(In the above formulas, X represents chlorine, bromine, or iodine.
And R represents an alkyl group having 1 to 20 carbon atoms, an aryl group,
Aralkyl group) and the like.

Specific examples of the sulfonyl halide compound having an alkenyl group include: o-, m-, p-CH ₂ ＣＨCH— (CH ₂ ) _n —C ₆ H
_{4 -SO 2 X, o-, m-} , p-CH 2 = CH- (CH 2) n -O-C
₆ H ₄ -SO ₂ X, (In each formula mentioned above, X is chlorine, bromine or iodine, n represents an integer of 0 to 20,), and the like. The organic halide having a crosslinkable silyl group is not particularly limited,
For example, those having the structure represented by the general formula (4) are exemplified. ^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2 -b (Y) b O] m -Si (R 12) 3- _a (Y) _a (4) (wherein, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and X are the same as described above, and R ¹¹ and R ¹² are each an alkyl group having 1 to 20 carbon atoms. , An aryl group, an aralkyl group, or (R ′) ₃
A triorganosiloxy group represented by SiO- (R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different); ,
When two or more R ¹¹ or R ¹² are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Ys are present, they may be the same or different. a
Represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. Where a + m
It satisfies that b ≧ 1)

The compound of the general formula (4) is specifically exemplified.
Then XCH₂C (O) O (CH₂)_nSi (OCH
₃)₃, CH₃C (H) (X) C (O) O (CH₂)_n
Si (OCH₃)₃, (CH₃)₂C (X) C (O) O
(CH₂)_nSi (OCH₃)₃, XCH₂C (O) O
(CH₂)_nSi (CH₃) (OCH₃)₂, CH₃C
(H) (X) C (O) O (CH₂)_nSi (CH₃)
(OCH₃)₂, (CH₃)₂C (X) C (O) O (C
H₂)_nSi (CH₃) (OCH₃)₂, (Each formula above
In the formula, X is chlorine, bromine, iodine, and n is an integer of 0 to 20.
Number,) XCH₂C (O) O (CH₂)_nO (CH₂)_mSi
(OCH₃)₃, H₃CC (H) (X) C (O) O (C
H₂)_nO (CH₂)_mSi (OCH₃) ₃, (H
₃C)₂C (X) C (O) O (CH₂)_nO (CH₂)
_mSi (OCH₃) ₃, CH₃CH₂C (H) (X) C
(O) O (CH₂)_nO (CH₂)_mSi (OCH₃)
₃, XCH₂C (O) O (CH₂)_nO (CH₂)_mS
i (CH₃) (OCH₃)₂, H₃CC (H) (X) C
(O) O (CH₂)_nO (CH₂)_m-Si (CH₃)
(OCH₃)₂, (H₃C)₂C (X) C (O) O (C
H₂)_nO (CH₂)_m-Si (CH₃) (OCH₃)
₂, CH₃CH₂C (H) (X) C (O) O (CH₂)
_nO (CH₂)_m-Si (CH₃) (OCH₃)₂,
(In each of the above formulas, X is chlorine, bromine, iodine, and n is
An integer of 1 to 20, m is an integer of 0 to 20)

O, m, p-XCH₂-C₆H₄− (CH
₂)₂Si (OCH₃)₃, O, m, p-CH₃C
(H) (X) -C₆H₄− (CH₂)₂Si (OC
H₃) ₃, O, m, p-CH₃CH₂C (H) (X)-
C₆H₄− (CH₂)₂Si (OCH₃)₃, O, m,
p-XCH₂-C₆H₄− (CH₂)₃Si (OC
H₃)₃, O, m, p-CH₃C (H) (X) -C₆H
₄− (CH₂)₃Si (OCH₃) ₃, O, m, p-C
H₃CH₂C (H) (X) -C₆H₄− (CH₂)₃S
i (OCH₃)₃, O, m, p-XCH₂-C₆H₄−
(CH₂)₂-O- (CH₂)₃Si (OCH₃)₃,
o, m, p-CH₃C (H) (X) -C₆H₄− (CH
₂)₂-O- (CH₂) ₃Si (OCH₃)₃, O,
m, p-CH₃CH₂C (H) (X) -C₆H₄− (C
H₂)₂-O- (CH₂)₃Si (OCH₃)₃, O,
m, p-XCH₂-C₆H₄-O- (CH₂)₃Si
(OCH₃)₃, O, m, p-CH₃C (H) (X)-
C₆H₄-O- (CH₂)₃Si (OCH ₃)₃, O,
m, p-CH₃CH₂C (H) (X) -C₆H₄-O-
(CH₂)₃-Si (OCH₃)₃, O, m, p-XC
H₂-C₆H₄-O- (CH₂)₂-O- (CH₂)₃
-Si (OCH₃)₃, O, m, p-CH₃C (H)
(X) -C₆H₄-O- (CH₂)₂-O- (CH ₂)
₃Si (OCH₃)₃, O, m, p-CH₃CH₂C
(H) (X) -C₆H₄-O- (CH₂)₂-O- (C
H₂)₃Si (OCH₃)₃, (In each of the above equations,
X is chlorine, bromine, or iodine).

Organic halogen having crosslinkable silyl group
The compound further has a structure represented by the general formula (5).
Are illustrated. (R¹²)_3-a(Y)_aSi- [OSi (R¹¹)_2-b(Y)_b]_m-CH ₂ -C (H) (R⁵) -R⁹-C (R⁶) (X) -R¹⁰-R⁷ (5) (where R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R
¹², A, b, m, X, and Y are the same as described above.₃
O)₃SiCH₂CH₂C (H) (X) C₆H₅, (C
H₃O)₂(CH₃) SiCH₂CH₂C (H) (X)
C₆H₅, (CH₃O)₃Si (CH₂)₂C (H)
(X) -CO₂R, (CH₃O)₂(CH₃) Si (C
H₂)₂C (H) (X) -CO₂R, (CH₃O)₃S
i (CH₂)₃C (H) (X) -CO₂R, (CH
₃O)₂(CH₃) Si (CH₂)₃C (H) (X)-
CO₂R, (CH₃O)₃Si (CH₂)₄C (H)
(X) -CO₂R, (CH₃O)₂(CH₃) Si (C
H₂)₄C (H) (X) -CO₂R, (CH₃O)₃S
i (CH₂)₉C (H) (X) -CO₂R, (CH
₃O)₂(CH₃) Si (CH₂)₉C (H) (X)-
CO₂R, (CH₃O)₃Si (CH₂)₃C (H)
(X) -C₆H₅, (CH₃O)₂(CH₃) Si (C
H₂)₃C (H) (X) -C₆H₅, (CH₃O)₃S
i (CH₂)₄C (H) (X) -C₆H₅, (CH
₃O)₂(CH₃) Si (CH₂)₄C (H) (X)-
C₆H₅, (In each of the above formulas, X represents chlorine, bromine,
Or iodine, R is an alkyl group having 1 to 20 carbon atoms, aryl
And aralkyl groups).

The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. HO- _{(CH 2)} in n -OC (O) C (H ) (R) (X) ( the formulas above, X is chlorine, bromine or iodine, R represents a hydrogen atom or an alkyl having 1 to 20 carbon atoms, Group,
An aryl group, an aralkyl group, and n is an integer of 1 to 20)

The organic halide having an amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. _{H 2 N- (CH 2) n} -OC (O) C (H) (R)
(X) (In each of the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
(Aryl group, aralkyl group, n is an integer of 1 to 20) The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

[0036]

Embedded image

(In each of the above formulas, X represents chlorine, bromine,
Or iodine and R are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20. Preferably, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. To give a concrete example,

[0038]

Embedded image

[0039]

Embedded image

And the like. There are no particular restrictions on the vinyl monomer used in this polymerization, and any of those already exemplified can be suitably used. The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably a group 7, 8, 9 or 10 of the periodic table.
A metal complex having a Group 11 or Group 11 element as a central metal. More preferred are zero-valent copper, monovalent copper,
Complexes of divalent ruthenium, divalent iron or divalent nickel. Among them, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. is there. When a copper compound is used, 2,2'-bipyridyl or its derivative, 1,10-phenanthroline or its derivative, or tetramethylethylenediamine, pentamethyldiethylenetriamine or hexamethyltris (2
(Aminoethyl) amine and other polyamines are added as ligands. In addition, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PP
h ₃ ) ₃ ) are also suitable as catalysts. When a ruthenium compound is used as a catalyst, aluminum alkoxides are added as an activator. Further, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ )
₂ ) Bivalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ) and divalent nickel bistributylphosphine complex (NiBr ₂ (PB
u ₃ ) ₂ ) are also suitable as catalysts.

The polymerization reaction can be carried out without a solvent, but can be carried out in various solvents. The type of solvent is not particularly limited, and examples thereof include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, and dimethoxybenzene; halogenated carbon solvents such as methylene chloride, chloroform, and chlorobenzene. Hydrogen solvent; acetone,
Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ethyl acetate , Butyl acetate and the like; ester solvents such as ethylene carbonate and propylene carbonate; N, N-dimethylformamide;
Amide solvents such as N-dimethylacetamide and the like can be mentioned. These may be used alone or in combination of two or more. Also, an emulsion or supercritical fluid CO ₂
Polymerization can also be carried out in a system using as a medium. Although not limited, the polymerization can be carried out in the range of 0 to 200 ° C, preferably in the range of room temperature to 150 ° C.

<Alkenyl group capable of hydrosilylation reaction>
>Alkenyl group  The alkenyl group in the present invention is not limited,
It is preferably represented by the general formula (7). H₂C = C (R¹³)-(7) (wherein, R¹³Represents hydrogen or an organic group having 1 to 20 carbon atoms.
You. In the general formula (7), R¹³Is hydrogen or carbon number 1-2
It is an organic group of 0. As an organic group having 1 to 20 carbon atoms,
Although not limited to, an alkyl group having 1 to 20 carbon atoms, carbon
Aryl group having 6 to 20 carbon atoms and aralkyl having 7 to 20 carbon atoms
Groups are preferred, and specific examples include the following groups.
You. − (CH₂)_n-CH₃, -CH (CH₃)-(C
H₂)_n-CH₃, -CH (CH₂CH₃)-(C
H₂)_n-CH₃, -CH (CH₂CH₃)₂, -C
(CH₃)₂− (CH₂)_n-CH₃, -C (CH₃)
(CH₂CH₃)-(CH₂)_n-CH₃, -C
₆H₅, -C₆H₅(CH₃), -C₆H₅(CH₃)
₂,-(CH₂)_n-C₆H₅,-(CH₂)_n-C₆
H₅(CH₃),-(CH₂)_n-C₆H₅(CH₃)
₂  (N is an integer of 0 or more, and the total number of carbon atoms of each group is 20 or less).¹³Is preferably a hydrogen or methyl group
Is more preferable.

Further, although not limited, the polymer (I)
Is preferably not activated by a carbonyl group, alkenyl group, or aromatic ring conjugated to the carbon-carbon double bond. The bonding form of the alkenyl group and the main chain of the polymer is not particularly limited, but may be a carbon-carbon bond, an ester bond, an ester bond, a carbonate bond,
It is preferable that they are bonded via an amide bond, a urethane bond, or the like.

[0044]Alkenyl group position  The cured product of the curable composition of the present invention particularly requires rubber-like properties.
If required, cross-linking has a significant effect on rubber elasticity
Since the molecular weight between points can be increased, the number of alkenyl groups
Preferably, one of them is at the terminal of the molecular chain. Better
Preferably, all alkenyl groups have at the terminal of the molecular chain.
It is. At least one alkenyl group at the molecular terminal
Vinyl polymer, especially (meth) acrylic polymer
The method for producing the union is disclosed in JP-B-3-14068,
JP-B-4-55444, JP-A-6-212922
No. 6,009,036. However, these methods
Is a free radical polymerization method using the above "chain transfer agent method"
Therefore, the obtained polymer has a relatively small alkenyl group.
While it has a high ratio at the molecular chain end, it is expressed as Mw / Mn.
The value of the molecular weight distribution is generally as large as 2 or more,
It has the problem of becoming expensive. Therefore, the molecular weight distribution
Is a low-viscosity vinyl polymer with a high proportion
To form a vinyl polymer having an alkenyl group at the molecular chain end.
In order to obtain, using the above "living radical polymerization method"
Preferably. The alkenyl group of the present invention is described below.
Will be explained.

<Alkenyl group introduction method>
The method of introducing an alkenyl group into the union is explained.
It is not limited to them.Introduction method of alkenyl group  (Aa) radical polymerization, preferably living radical
When synthesizing a vinyl polymer by polymerization, for example,
Polymerizable in one molecule as listed in the general formula (9)
Combination of alkenyl group and alkenyl group with low polymerizability
A method in which the compound is reacted as a second monomer. H₂C = C (R¹⁴) -R^Fifteen-R¹⁶-C (R¹⁷) = CH₂ (9) (where R¹⁴Represents hydrogen or a methyl group;^FifteenIs
-C (O) O-, or o-, m-, p-phenylene group
And R¹⁶Is a direct bond or 2 having 1 to 20 carbon atoms
A valent organic group containing one or more ether linkages
You may. R¹⁷Represents hydrogen or an organic group having 1 to 20 carbon atoms
Show)

In the general formula (9), R¹⁷Is hydrogen or
It is an organic group having 1 to 20 carbon atoms. Organic having 1 to 20 carbon atoms
The group is not particularly limited, but may have 1 to 20 carbon atoms.
Kill group, aryl group having 6 to 20 carbon atoms, 7 to 20 carbon atoms
The aralkyl group is preferably, specifically, a group such as
Is exemplified. − (CH₂)_n-CH₃, -CH (CH₃)-(C
H₂)_n-CH₃, -CH (CH₂CH₃)-(C
H₂)_n-CH₃, -CH (CH₂CH₃)₂, -C
(CH₃)₂− (CH₂)_n-CH₃, -C (CH₃)
(CH₂CH₃)-(CH₂)_n-CH₃, -C
₆H₅, -C₆H₅(CH₃), -C₆H₅(CH₃)
₂,-(CH₂)_n-C₆H₅,-(CH₂)_n-C₆
H₅(CH₃),-(CH₂)_n-C₆H₅(CH₃)
₂  (N is an integer of 0 or more, and the total number of carbon atoms of each group is 20 or less).¹⁷Is preferably a hydrogen or methyl group
Is more preferable. In addition, a polymerizable alkenyl group in one molecule
Reacting a compound having an alkenyl group with low polymerizability
There is no restriction on the time, especially in living radical polymerization,
The end of the polymerization reaction or when rubbery properties are expected
Is the second monomer after completion of the reaction of the given monomer.
Preferably, the reaction is carried out.

(Ab) When a vinyl-based polymer is synthesized by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, A method of reacting a compound having at least two alkenyl groups having low polymerizability, such as 9-decadiene. (Ac) Various organic metal compounds having an alkenyl group such as an organic tin such as allyltributyltin and allyltrioctyltin are added to a vinyl polymer having at least one highly reactive carbon-halogen bond. A method of substituting halogen by reacting.

(Ad) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having an alkenyl group as shown in the general formula (10) to form a halogen. How to replace. ^{M + C - (R 18)} (R 19) -R 20 -C (R 17) = CH 2 (10) ( ^{wherein, R 17} same ^.R 18 in the ^{above, R 19} together carbanion C ^- stable Or one of them is the above-mentioned electron-withdrawing group and the other is hydrogen or carbon atom 1
Represents an alkyl group of 10 to 10 or a phenyl group. R ²⁰
Represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds. M ⁺
Represents an alkali metal ion or a quaternary ammonium ion. Examples of the electron withdrawing groups for R ¹⁸ and R ¹⁹ include —CO ₂ R (ester group), —C (O) R (keto group), and —CON.
_(R 2) (amide group), - COSR (thioester group), - CN (nitrile group), - NO ₂ is (nitro group), and the _{like, -CO 2 R, -C (O} ) R and -C
N is particularly preferred. Note that the substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
10 alkyl groups or phenyl groups.

(Ae) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a simple metal such as zinc or an organometallic compound. An alkenyl group-containing electrophilic compound such as an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, and an acid halide having an alkenyl group. How to react. (Af) A vinyl polymer having at least one highly reactive carbon-halogen bond may, for example, be a compound represented by the general formula (11):
Alternatively, a method of reacting an oxyanion or a carboxylate anion having an alkenyl group as shown in (12) to replace halogen. _{^{H 2 C = C (R 17}} ) -R 21 -O - M + (11) ( ^wherein, same ^{.R 21} to R 17, ^{M +} is above 1 -C
H ₂ C = C (R ¹⁷ ) -R ²² -C (O) O ^- M ⁺ (12) wherein the divalent organic group may have one or more ether bonds. R ¹⁷ and M ⁺ are the same as described above, and R ²² is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds.
In the present invention, when halogen is not directly involved in the method for introducing an alkenyl group such as (Aa) and (Ab),
As a method for synthesizing a vinyl polymer, a living radical polymerization method is preferable, and an atom transfer radical polymerization method is more preferable.

In a method using a vinyl polymer having at least one highly reactive carbon-halogen bond as described in (Ac) to (Af), a highly reactive carbon-halogen is used. As a method for synthesizing a vinyl polymer having at least one bond, a chain transfer polymerization method using a halide as a chain transfer agent or an atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator is preferable. Transfer radical polymerization is more preferred. Among the methods (Aa) to (Af), the methods (Ab) and (Af) are preferable because the control is easier. Hereinafter, the method of introducing (Ab) and (Af) will be described in detail.

[0051]Diene compound addition method [(Ab) method]  The method (Ab) uses a living radical of a vinyl monomer.
The vinyl polymer obtained by polymerization has low polymerizability
Compounds having at least two kenyl groups (hereinafter referred to as diene
It is called a compound. ) Is reacted. Jie
At least two alkenyl groups of the compound
Or it may be different. As the alkenyl group,
Lucenyl group [CH₂= C (R) -R '; R is hydrogen or charcoal
An organic group having a prime number of 1 to 20, R 'is an organic group having a carbon number of 1 to 20
R and R 'are bonded to each other to form a cyclic structure
You may. ] Or an internal alkenyl group [R'-C (R) =
C (R) -R '; R is hydrogen or an organic group having 1 to 20 carbon atoms
R ′ is an organic group having 1 to 20 carbon atoms, and two R groups
Or two R's may be the same or different
May be. Any two of two R and two R '
May be bonded to each other to have a cyclic structure. No
Although it may be shifted, a terminal alkenyl group is more preferable. R
Is hydrogen or an organic group having 1 to 20 carbon atoms,
As the organic group having from 20 to 20, an alkyl group having from 1 to 20 carbon atoms,
Aryl group having 6 to 20 carbon atoms, aral having 7 to 20 carbon atoms
Kill groups are preferred. Among them, R is hydrogen or
A methyl group is particularly preferred. In addition, alkene diene compounds
At least two of the alkenyl groups are conjugated
It may be. Specific examples of the diene compound include, for example,
Isoprene, piperylene, butadiene, myrcene, 1,
5-hexadiene, 1,7-octadiene, 1,9-de
Cadien, 4-vinyl-1-cyclohexene and the like.
1,5-hexadiene, 1,7-octadie
1,9-decadiene is preferred.

Living vinyl polymerization of a vinyl monomer is carried out, and the obtained polymer is isolated from the polymerization system. Then, the isolated polymer is subjected to a radical reaction with a diene compound to thereby form an alkenyl group at a desired terminal. Although it is possible to obtain a vinyl polymer having the polymer, it is more preferable to add a diene compound to the polymerization reaction system at the end of the polymerization reaction or after the completion of the reaction of a predetermined vinyl monomer. The amount of the diene compound added needs to be adjusted by the radical reactivity of the alkenyl group of the diene compound. When there is a large difference in the reactivity of the two alkenyl groups, the diene compound may be in an equivalent amount or a small excess with respect to the polymerization growth terminal. Since both groups react and the polymerization ends are coupled,
The amount of the diene compound added is preferably an excess amount relative to the polymer growing terminal, preferably 1.5 times or more, more preferably 3 times or more, and particularly preferably 5 times or more.

[0053]Nucleophilic substitution method ((Af) method)  The method (Af) reduces the number of highly reactive carbon-halogen bonds.
An alkenyl group is contained in at least one vinyl polymer.
Oxy or carboxylate anions
To replace halogen. A
Oxyanion or carboxylate having a alkenyl group
The anion is not particularly limited, for example, the general formula
(11) or (12)
You. H₂C = C (R¹⁷) -R²¹-O⁻M⁺ (11) (where R¹⁷, M⁺Is the same as above. R²¹Is 1 carbon
~ 20 divalent organic groups containing one or more ether linkages
H)₂C = C (R¹⁷) -R²²-C (O) O⁻M⁺ (12) (where R¹⁷, M⁺Is the same as above. R²²Is directly tied
Or one or more divalent organic groups having 1 to 20 carbon atoms.
(It may contain an ether bond)

Specific examples of the oxyanion or carboxylate anion include metal salts or quaternary ammonium salts of alkenyl alcohols such as allyl alcohol; metal salts or quaternary ammonium salts of allyloxy alcohols such as ethylene glycol monoallyl ether. ;
Metal salts or quaternary ammonium salts of alkenyl-containing phenolic hydroxyl groups such as allylphenol and allyloxyphenol; metal salts or quaternary ammonium salts of alkenyl-containing carboxylic acids such as 10-undecylenic acid, 4-pentenoic acid and vinylacetic acid And the like.

M ⁺ is a counter cation, and the type of M ⁺ is an alkali metal ion, specifically, a lithium ion;
Sodium ion, potassium ion, and quaternary ammonium ion. Examples of the quaternary ammonium ion include a tetramethylammonium ion, a tetraethylammonium ion, a tetrabenzylammonium ion, a trimethyldodecylammonium ion, a tetrabutylammonium ion, and a dimethylpiperidinium ion, and a sodium ion and a potassium ion are preferable. The amount of the oxyanion or carboxylate anion used may be an excess with respect to the halogen, preferably 1 to 5 equivalents, more preferably 1 to 5 equivalents.
It is 2 equivalents, more preferably 1.0 to 1.2 equivalents.

The solvent for carrying out this reaction is not particularly limited, but is preferably a solvent having a relatively high polarity, for example, ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; methylene chloride, chloroform and the like. Halogenated hydrocarbon solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; methanol,
Alcohol solvents such as ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; ethylene carbonate, propylene Carbonate solvents such as carbonate; amide solvents such as dimethylformamide and dimethylacetamide; and sulfoxide solvents such as dimethylsulfoxide. These can be used alone or in combination of two or more. Among them, polar solvents such as acetone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, and acetonitrile are more preferable. Although the reaction temperature is not limited, it is generally 0 to 150 ° C, more preferably room temperature to 100 ° C.

Further, amines, ammonium salts, crown ethers and the like may be added to the reaction system as a reaction accelerator. The oxyanion or carboxylate anion may be prepared by reacting with a base in a reaction system using a precursor alcohol or carboxylic acid instead of the oxyanion or carboxylate anion. Use of a carboxylate anion with low nucleophilicity because the use of a highly nucleophilic oxyanion may cause transesterification when an ester group is present in the side chain of the vinyl polymer or in the main chain. Is more preferred.

[0058]Method for converting hydroxyl group to alkenyl group  Vinyl polymer having at least one alkenyl group
Is from a vinyl polymer having at least one hydroxyl group.
It is also possible to use the methods exemplified below.
However, the present invention is not limited to these. Less hydroxyl groups
(Ag) A base such as sodium methoxide is acted on a hydroxyl group of a vinyl polymer having at least one of them.
Alkenyl group-containing halides such as allyl chloride
How to react with. (Ah) containing alkenyl group such as allyl isocyanate
A method of reacting an isocyanate compound. (Ai) Alke such as (meth) acrylic acid chloride
Nyl group-containing acid halide in the presence of a base such as pyridine
How to react. (Aj) Alkenyl group-containing carboxylic acids such as acrylic acid
In the presence of an acid catalyst.

(Ak) A method in which a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group, and a compound having both an alkenyl group and a hydroxyl group in the remaining isocyanate group is reacted. The compound having both an alkenyl group and a hydroxyl group is not particularly limited, and examples thereof include alkenyl alcohols such as 10-undecenol, 5-hexenol, and allyl alcohol. The diisocyanate compound is not particularly limited, and any conventionally known diisocyanate compound can be used. , 5
-Isocyanate compounds such as naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; These can be used alone or in combination of two or more. Further, a blocked isocyanate may be used. To take advantage of better weather resistance, for example, hexamethylene diisocyanate,
It is preferable to use a diisocyanate compound having no aromatic ring such as hydrogenated diphenylmethane diisocyanate.

[0060]Method for synthesizing vinyl polymer having hydroxyl group  (B) and water used in the methods (Ag) to (Aj)
Method for producing vinyl polymer having at least one acid group
The following methods are exemplified, but these methods are
It is not specified. (Ba) Synthesizing a vinyl polymer by radical polymerization
In this case, for example, as shown in the following general formula (15)
Has a polymerizable alkenyl group and a hydroxyl group in one molecule
A method in which a compound is reacted as a second monomer. H₂C = C (R¹⁴) -R^Fifteen-R¹⁶—OH (15) (wherein, R¹⁴, R^Fifteen, R¹⁶The same applies to the above.) In addition, a polymerizable alkenyl group and a hydroxyl group are combined in one molecule.
There are no restrictions on the timing of the reaction of compounds with
When expecting rubber-like properties in radical polymerization,
At the end of the polymerization reaction or after the end of the reaction of the specified monomer
Is preferably reacted as a second monomer. (Bb) Vinyl polymer by living radical polymerization
At the end of the polymerization reaction or when the desired monomer is synthesized.
After completion of the reaction, for example, 10-undecenol,
Alkenyl alcohols such as hexenol and allyl alcohol
How to react rucol.

(Bc) For example, Japanese Patent Application Laid-Open No. 5-262808
A radical polymerization of a vinyl monomer using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide shown in (1). (Bd) For example, JP-A-6-239912, JP-A-8-
A method of radically polymerizing a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as shown in 283310. (Be) A method in which a vinyl monomer is radically polymerized using an excess of alcohols as described in, for example, JP-A-6-11612. (Bf) Hydrolyzing or reacting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond with a hydroxyl group-containing compound by a method described in, for example, JP-A-4-132706. By introducing a hydroxyl group into the terminal.

(Bg) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group as shown in the general formula (16) to substitute halogen. how to. ^{M + C - (R 18)} (R 19) -R 20 -OH (16) as an electron withdrawing group ^{(wherein, R 18, R 19, R} 20, are the same) ^{R 18, R 19} are, —CO ₂ R (ester group), —C (O) R (keto group), —CON
_(R 2) (amide group), - COSR (thioester group), - CN (nitrile group), - NO ₂ is (nitro group), and the _{like, -CO 2 R, -C (O} ) R and -C
N is particularly preferred. Note that the substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
10 alkyl groups or phenyl groups.

(Bh) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a simple metal such as zinc or an organometallic compound. A method of reacting aldehydes or ketones later. (Bi) A vinyl polymer having at least one carbon-halogen bond having high reactivity, for example, a compound represented by the general formula (17)
Alternatively, a method of reacting an oxyanion or a carboxylate anion having a hydroxyl group as shown in 18 to replace halogen. ^{HO-R 21 -O - M +} (17) ( ^{wherein, R 21} and ^{M +} are the ^{same) HO-R 22 -C (O} ) O - M + (18) ( ^{wherein, R 22} and M ⁺ Is the same as above.) As for M ⁺ , reaction conditions, solvents and the like, all those described in the description of (A-f) can be suitably used.

(Bj) When a vinyl polymer is synthesized by living radical polymerization, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, alkenyl having a low polymerizability in one molecule is used as a second monomer. A method of reacting a compound having a group and a hydroxyl group. Such a compound is not particularly limited, and examples thereof include a compound represented by the general formula (19). _{^{H 2 C = C (R 14}} ) -R 21 -OH (19) ( ^{wherein, R 14} and ^{R 21} are the same as those described above.) In particular limitation is imposed on the compound represented by the above general formula (19) Not available, but 10-
Alkenyl alcohols such as undecenol, 5-hexenol, allyl alcohol are preferred.

In the present invention, when a halogen is not directly involved in the method for introducing a hydroxyl group such as (Ba) to (Be) and (Bj), a living method is used as a method for synthesizing a vinyl polymer. A radical polymerization method is preferred, and an atom transfer radical polymerization method is more preferred. (Bf) to (Bi)
In the method using a vinyl polymer having at least one highly reactive carbon-halogen bond as described in the above, the method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond A chain transfer polymerization method using a halide as a chain transfer agent or an atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator is preferable, and an atom transfer radical polymerization method is more preferable. (Ba) to (B-
Among the synthesis methods j), the methods (Bb) and (Bi) are preferable because the control is easier.

<< Regarding Hydrosilyl Group-Containing Compound (II) >> As the hydrosilyl group-containing compound as the component (B), hydrosilyl curable by crosslinking with the vinyl polymer having at least one alkenyl group as the component (A) There is no particular limitation as long as it is a group-containing compound, and various compounds can be used. Among them organohydrogenpolysiloxane is preferred, for example, chain polysiloxanes represented by the general formula (22) or _{^{(23); R 23 3 SiO-}} [Si (R 23) 2 O] a - [Si (H _{^{) (R 24) O] b}} - [Si (R 24) (R 25) O] c -SiR 23 3 (22) HR 23 2 SiO- [Si (R 23) 2 O] a - [Si (H) _{^{(R 24) O] b -}} [Si (R 24) (R 25) O] c -SiR 23 2 H (23) ( ^{wherein, R 23} and ^{R 24} is an alkyl group having 1 to 6 carbon atoms, or A phenyl group and R ²⁵ represent an alkyl group or an aralkyl group having 1 to 10 carbon atoms, and a represents 0 ≦ a ≦ 10.
0 and b are integers satisfying 2 ≦ b ≦ 100, and c is an integer satisfying 0 ≦ c ≦ 100. A cyclic siloxane represented by the general formula (24);

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(Where R²⁶And R²⁷Has 1 to 1 carbon atoms
6, an alkyl group or a phenyl group, R²⁸Is the carbon number
1 to 10 alkyl groups or aralkyl groups. d is
0 ≦ d ≦ 8, e is 2 ≦ e ≦ 10, f is an integer of 0 ≦ f ≦ 8
And satisfies 3 ≦ d + e + f ≦ 10. ) Etc.
Compounds can be used. Even if these are used alone,
A mixture of more than one species may be used. These shiroki
View of compatibility with (meth) acrylic polymer even among sun
From the viewpoint, the following general formulas (25) and (2) having a phenyl group
The chain siloxane represented by 6), the general formula (27),
The cyclic siloxane represented by (28) is preferable. (CH₃)₃SiO- [Si (H) (CH₃) O]_g− [Si (C₆H₅)₂O]_h-Si (CH₃)₃ (25) (CH₃)₃SiO- [Si (H) (CH₃) O]_g− [Si (CH₃) ｛CH ₂ C (H) (R²⁴) C₆H₅｝ O]_h-Si (CH₃)₃ (26) (where R²⁴Represents hydrogen or a methyl group. g is 2 ≦
g ≦ 100 and h indicate an integer of 0 ≦ h ≦ 100. C₆H
₅Represents a phenyl group. )

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(Wherein R ²⁹ represents hydrogen or a methyl group. I is 2 ≦ i ≦ 10, j is 0 ≦ j ≦ 8, and 3 ≦ i
An integer satisfying + j ≦ 10 is shown. C ₆ H ₅ represents a phenyl group. As the compound having at least one hydrosilyl group of the component (B), a low molecular weight compound having two or more alkenyl groups in the molecule may further be selected from hydrosilyl groups represented by the general formulas (22) to (28). A compound obtained by subjecting a group-containing compound to an addition reaction so that some hydrosilyl groups remain even after the reaction can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, 1,4
Hydrocarbon compounds such as -pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene and 1,9-decadiene;
O'-diallylbisphenol A, ether compounds such as 3,3'-diallylbisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate and tetraallyl pyromellitate, diethylene glycol diallyl carbonate and the like And carbonate-based compounds. The general formula (2)
The compound can be obtained by slowly dropping the above-mentioned alkenyl group-containing compound in excess of the hydrosilyl group-containing compound shown in 2) to (28) in the presence of a hydrosilylation catalyst. Among these compounds, the following compounds are preferred in consideration of the availability of raw materials, the ease of removing excess siloxane, and the compatibility with the vinyl polymer (I).

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<< About the Organometallic Compound (III) >>
> The organometallic compound (III) in the present invention is not particularly limited as long as it is any one of an organoaluminum compound, an organotitanium compound and an organotin compound, and examples thereof include the following. Aluminum organolate (trialkoxy aluminum) among organic aluminum compounds
As classes, for example, aluminum isopropylate,
Mono-sec-butoxyaluminum diisopropylate,
Aluminum sec-butylate and the like. Examples of the aluminum chelates include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), and aluminum monoacetyl acetonate bis (ethyl aceto acetate). Among them, aluminum chelates are preferred.

As the organotitanium compound, an organotitanium compound having a Ti—O—C bond, which is a useful catalyst for the hydrolysis-condensation reaction of an alkoxysilyl group, is preferred. Specific examples include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium, and general titanate coupling agents such as those having a residue such as oxyacetic acid and ethylene glycol. Further, examples of the organotin compound include compounds which are useful catalysts for the hydrolysis-condensation reaction of alkoxysilyl groups, and among them, organotin compounds having an alkoxyl group such as dibutyltin dimethoxide are preferred.

On the other hand, the amount of the organometallic compound (III) is not particularly limited, but is 0.01 to 100 parts by weight, preferably 0.0 to 100 parts by weight, per 100 parts by weight of the vinyl polymer (I).
5 to 50 parts by weight, more preferably 0.1 to 30 parts by weight,
It is more preferable to use 0.1 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight. In general, these organometallic compounds are expensive, and the effect of lowering the viscosity can be seen when used in a small amount, and when used in an excessively large amount, the physical properties are deteriorated. Further, the organometallic compound (III) of the present invention may be used alone,
Two or more kinds may be used in combination.

<< Inorganic Filler (IV) >> The inorganic filler (IV) that can be blended is not particularly limited.
In order to impart physical properties such as strength, for example, fine powdered silica, calcium carbonate, talc, titanium oxide, diatomaceous earth, barium sulfate, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activated zinc white are exemplified. The inorganic fillers may be used alone or in combination of two or more. Among these, silica fine powder is preferable, and hydrated silica obtained by a wet production method or the like, dry silica obtained by a dry production method or the like can be used. Of these, anhydrous silica is particularly preferred because if the composition contains a large amount of water, a side reaction or the like may occur during the curing reaction. Further, those obtained by subjecting the surface of anhydrous silica to a hydrophobic treatment are particularly preferred because they easily exhibit fluidity suitable for molding. In addition, an inorganic filler that is not so strong in reinforcement may be used for increasing the amount or adjusting the physical properties. The amount of the inorganic filler (IV) is not particularly limited, but is usually 1 to 500 parts by weight, preferably 10 to 300 parts by weight, per 100 parts by weight of the vinyl polymer (I).
Parts by weight. The inorganic filler (IV) may be used alone or in combination of two or more.

<< Curable Composition >> In the curable composition of the present invention, various additives for adjusting physical properties, for example,
Flame retardants, anti-aging materials, plasticizers, physical property modifiers, adhesion promoters, storage stability improvers, solvents, radical inhibitors, metal deactivators, ozone deterioration inhibitors, phosphorus peroxide decomposers,
A lubricant, a pigment, a foaming agent, a photocurable resin, and the like may be appropriately compounded as necessary. These various additives may be used alone or in combination of two or more. Further, since the vinyl polymer is originally a polymer having excellent durability, an antioxidant is not necessarily required, but conventionally known antioxidants, ultraviolet absorbers, light stabilizers and the like may be appropriately used. it can.

<Plasticizer> The plasticizer that can be blended is not particularly limited. For example, dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate may be used for the purpose of adjusting physical properties and adjusting properties. Non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; Polyalkylene glycol esters such as benzoate, triethylene glycol dibenzoate, and pentaerythritol ester; phosphates such as tricresyl phosphate and tributyl phosphate; trimellitate; Polystyrenes such as rene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; Polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; and polyethers such as derivatives in which hydroxyl groups of these polyether polyols are converted into ester groups, ether groups, and the like; epoxidized soybean oil, benzyl epoxy stearate And other dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Polyester plasticizers obtained from dihydric alcohols such as propylene glycol; vinyl polymers obtained by polymerizing vinyl monomers such as acrylic plasticizers by various methods; 1-octene, 4-vinyl Reactive plasticizers such as cyclohexene, allyl acetate, 1,1-diacetoxy-2-propene, methyl 1-undecenoate, 8-acetoxy-1,6-octadiene, etc. may be used alone or as a mixture of two or more. Is possible, but not necessary. In addition, these plasticizers can be blended at the time of polymer production. The amount of the plasticizer used is not limited, but is added to improve the fluidity of the composition, and may be selected from the group consisting of an organoaluminum compound and / or an organotitanium compound and / or an organotin compound (III). It is preferable to use it within a range that does not hinder the effect.

<Storage Stability Improver> The storage stability improver that can be blended is not particularly limited as long as it can suppress the increase in the viscosity of the composition during storage and the remarkable change in the curing rate after storage. For example, benzothiazole, dimethyl malate and the like can be mentioned.

<Solvent> Solvents that can be blended are, for example, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve, methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone. And the like. These solvents may be used during the production of the polymer.

<Adhesiveness-imparting agent> As the adhesiveness-imparting agent that can be blended, any one can be used as long as it imparts adhesiveness to a cured product obtained by crosslinking the vinyl polymer (I) and the hydrosilyl group-containing compound (II). Although not particularly limited, a crosslinkable silyl group-containing compound is preferable, and a silane coupling agent is more preferable. Specific examples thereof include alkyl alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; alkyls such as dimethyldiisopropenoxysilane and methyltriisopropenoxysilane. Isopropenoxysilanes; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acroyloxypropylmethyltriethoxysilane; Silicone varnishes; polysiloxanes and the like.

Among them, organic groups having atoms other than carbon atoms and hydrogen atoms such as epoxy group, (meth) acryl group, isocyanate group, isocyanurate group, carbamate group, amino group, mercapto group and carboxyl group in the molecule. And a silane coupling agent having a crosslinkable silyl group. When these are specifically exemplified, alkoxysilanes having an isocyanate group include γ-
Isocyanate group-containing silanes such as isocyanate propyl trimethoxy silane, γ-isocyanate propyl triethoxy silane, γ-isocyanate propyl methyl diethoxy silane, γ-isocyanate propyl methyl dimethoxy silane; alkoxysilanes having an isocyanurate group include: Isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate;
Examples of the alkoxysilane having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, and N- (β-aminoethyl ) -Γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane,
N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, Amino group-containing silanes such as N-vinylbenzyl-γ-aminopropyltriethoxysilane; alkoxysilanes having a mercapto group include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyl Mercapto group-containing silanes such as methyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; and alkoxysilanes having a carboxyl group include β-
Carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane,
Carboxysilanes such as N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; alkoxysilanes having a halogen group include
halogen-containing silanes such as γ-chloropropyltrimethoxysilane;

Further, derivatives of these modified amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones and silylated polyesters are also used as silane coupling agents. be able to. Further, among these, in terms of curability and adhesiveness,
Alkoxysilanes having an epoxy group or a (meth) acryl group in the molecule are more preferred. When these are more specifically exemplified, alkoxysilanes having an epoxy group include γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, etc. are represented by (meth) acrylic groups. Examples of the alkoxysilanes having: γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane And methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, and the like. These may be used alone or in combination of two or more.

Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include an epoxy resin, a phenol resin, sulfur, and an aromatic polyisocyanate. The adhesiveness-imparting agent is a vinyl polymer (I) 1
It is preferable to add 0.01 to 20 parts by weight to 00 parts by weight. If the amount is less than 0.01 part by weight, the effect of improving the adhesion is small, and if it exceeds 20 parts by weight, the physical properties of the cured product are adversely affected. Preferably it is 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. The above-mentioned adhesiveness imparting agent may be used alone or in combination of two or more. The addition of these adhesion-imparting agents can improve the adhesion to the adherend.

<< Method for Preparing Cured Product >> The vinyl polymer (I) and the hydrosilyl group-containing compound (II) can be mixed in any ratio, but from the viewpoint of curability, an alkenyl group and a hydrosilyl group are mixed. Is preferably in the range of 5 to 0.2, and more preferably 2.5 to 0.4. When the molar ratio is 5 or more, only a cured product of insufficient strength with insufficient tackiness and stickiness can be obtained,
On the other hand, if it is smaller than 0.2, 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 cannot be obtained.

The curing reaction between the vinyl polymer (I) and the hydrosilyl group-containing compound (II) proceeds by mixing and heating the two components. To accelerate the reaction, a hydrosilylation catalyst is used. Can be added.
Such a hydrosilylation catalyst is not particularly limited, and examples thereof include a radical initiator such as an organic peroxide and an azo compound, and a transition metal catalyst.

The radical initiator is not particularly limited.
For example, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
Such as 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy) isopropylbenzene Dialkyl peroxides, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate, Peroxydicarbonates such as diisopropyl carbonate, di-2-ethylhexyl percarbonate, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3,5-trimethyl Peroxyke such as cyclohexane It can be mentioned Lumpur and the like.

The transition metal catalyst is not particularly limited. For example, a platinum solid, a dispersion of platinum solid in a carrier such as alumina, silica, carbon black or the like, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, Examples include a complex with a ketone, a platinum-olefin complex, and a platinum (0) -divinyltetramethyldisiloxane complex. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ ,
RhCl ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , A
lCl ₃ , PdCl ₂ .H ₂ O, NiCl ₂ , TiCl
_{4 and the} like. These catalysts may be used alone or in combination of two or more. The amount of the catalyst is not particularly limited, but 1 mol of the alkenyl group of component (A)
It is good to use in the range of 10 ^-1 to 10 ^-8 mol, preferably in the range of 10 ^-3 to 10 ^-6 mol with ^respect to 1. If the amount is less than 10 ⁻⁸ mol, the curing does not proceed sufficiently. Also, the hydrosilylation catalyst is generally expensive and corrosive, and it is preferable not to use more than 10 ^-1 mol because a large amount of hydrogen gas is generated and a cured product may foam.

The curing temperature is not particularly limited, but it is generally preferable to cure at 0 ° C. to 200 ° C., preferably 30 ° C. to 150 ° C., more preferably 80 ° C. to 150 ° C. Thereby, a curable composition can be obtained in a short time.

<< Molding Method >> The molding method when the curable composition of the present invention is used as a molded article is not particularly limited, and various commonly used molding methods can be used. For example, cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, thermoforming and the like can be mentioned. In particular, injection molding is preferred from the viewpoint that automation and continuity are possible and productivity is excellent. In addition, when used as a gasket, etc., both a wet type where the curable composition applied to the flange surface etc. is sandwiched from both sides in an uncured state and then cured, and a dry type where the cured composition is sandwiched after being cured are possible It is.

<< Use >> The curable composition of the present invention is not limited, but is used for electric / electronics such as a sealing material in an elastic sealing material for buildings and a sealing material for double glazing, and a sealing material for a back surface of a solar cell. Parts materials, electrical insulating materials such as insulating coatings for wires and cables, adhesives, adhesives, elastic adhesives, paints, powder coatings, coatings, foams, potting materials for electric and electronic devices, films, gaskets, casting It can be used for various purposes, such as materials, artificial marble, various molding materials, and netted glass and rustproof / waterproof sealing materials for laminated glass end faces (cut portions).

Further, the molded article having rubber elasticity obtained from the curable composition of the present invention can be widely used mainly for gaskets and packings. For example, in the field of automobiles, it can be used as a body part as a sealing material for maintaining airtightness, a vibration preventing material for glass, a vibration damping material for a body part, particularly a window seal gasket, a gasket for door glass. As a chassis component, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubber. As engine parts, it can be used for hoses for cooling, fuel supply, exhaust control, etc., seals for engine oil, and the like. It can also be used for exhaust gas purifier parts and brake parts. In the field of home appliances, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting equipment, waterproof packings, vibration-proof rubbers, insect-proof packings, vibration-proof and sound-absorbing and air-sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packing, heater parts Packing, electrode part packing, safety valve diaphragm, hoses for sake kettle, waterproof packing, solenoid valve, waterproof packing for steam oven range and jar rice cooker, water supply tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Heater packing, oil packing for combustion equipment such as steam outlet seal, O-ring, drain packing, pressurizing tube, blower tube, sending / suction packing, anti-vibration rubber,
Examples include a filler gasket, a speaker edge, a turntable sheet, a belt, a pulley, and the like for audio equipment, such as a filler port packing, an oil meter packing, an oil supply pipe, a diaphragm valve, and an air supply pipe. In the construction field, structural gaskets (zipper gaskets), air film structural roofing materials,
It can be used for waterproof material, fixed sealing material, vibration-proof material, sound-proof material, setting block, sliding material, etc. In the field of sports, it can be used for sports floors such as all-weather pavement materials, gymnasium floors, etc., for sports shoes for shoe sole materials and midsole materials, and for ball balls for golf balls and the like. In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, fenders and the like. In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings,
Rubber molds, rubber packers, rubber skirts, sponge mats, mortar hoses, mortar strainers, etc. as construction auxiliary materials such as waterproof sheets, rubber dams, elastic pavements, vibration proof pads, protective bodies, etc., rubber sheets, air hoses, etc. as construction auxiliary materials It can be used for rubber buoys and wave absorbers as safety measures products, and for oil fences, silt fences, antifouling materials, marine hoses, dressing hoses, oil skimmers and the like as environmental protection products. In addition, it can be used for rubber plate, mat, foam plate and the like.

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EXAMPLES Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively. In the following examples, "number average molecular weight" and "molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)" were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, GP
Two columns packed with polystyrene cross-linked gel as a C column (shodex GPC K-802.5; manufactured by Showa Denko KK) (shodex GPC K-804; manufactured by Showa Denko KK) are used in series, and GPC is used. Chloroform was used as a solvent.

(Production Example 1) 1 equipped with a reflux tube and a stirrer
In a 0 L separable flask, put CuBr (36.02).
g, 0.2511 mol), and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (618 mL) was added, and the mixture was stirred at 70 ° C. for 15 minutes in an oil bath. To this, butyl acrylate (360 mL, 2.51 mol), ethyl acrylate (500 mL, 4.62 mol), acrylic acid 2-
Methoxyethyl (375 mL, 2.91 mol), 2,
Diethyl 5-dibromoadipate (150.68 g,
0.419 mol), pentamethyldiethylenetriamine (2.18 mL, 1.81 g, 10.46 mmol)
(Hereinafter triamine) was added to initiate the reaction. While heating and stirring at 70 ° C., butyl acrylate (1
A mixture of 440 mL), ethyl acrylate (2002 mL), and 2-methoxyethyl acrylate (1498 mL) was continuously dropped over 210 minutes. During the dropping of the monomer, triamine (7.63 mL, 6.33 g, 36.5) was used.
mmol) was added. After 330 minutes from the start of the reaction, 1,7-octadiene (1236 mL, 922 g, 8.
37 mol), triamine (26.16 mL, 21.7)
1 g, 0.125 mol), and then added at 70 ° C. for 2 hours.
The mixture was heated and stirred for 50 minutes.

After diluting the reaction mixture with toluene and passing through an activated alumina column, the volatile components are distilled off under reduced pressure to obtain an alkenyl-terminated copolymer ｛alkenyl-terminated poly (butyl acrylate, ethyl acrylate, methoxy acrylate). Ethyl) copolymer: Copolymer [1]｝ was obtained. In a 10 L separable flask equipped with a reflux tube, copolymer [1]
(2.87 kg), potassium acetate (79.57 g),
N, N-dimethylacetamide (2.9 L) was charged, and the mixture was heated and stirred at 100 ° C. for 12 hours under a nitrogen stream. After removing N, N-dimethylacetic acid amide under reduced pressure by heating, the mixture was diluted with toluene. The solids insoluble in toluene (KBr and excess potassium acetate) were filtered through an activated alumina column.
The copolymer [2] is obtained by distilling off the volatile components of the filtrate under reduced pressure.
I got In a 10 L separable flask equipped with a reflux tube, the copolymer [2] (2.87 kg) and the acidic aluminum silicate (143) were placed.
g, Kyoward 700SL), basic aluminum silicate (143g, Kyowa 500, Kyoward 500)
SH) and toluene (5.2 L) were charged under a nitrogen stream.
The mixture was heated and stirred at 00 ° C. for 7 hours. After removing the aluminum silicate by filtration, toluene in the filtrate was distilled off under reduced pressure to obtain a vinyl group-terminated copolymer (copolymer [3]). The number average molecular weight of the obtained copolymer was 18,000 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.24. The average number of vinyl groups introduced per copolymer molecule was determined by ¹ H NMR analysis.
There were two.

Example 1 100 g of the copolymer [3] obtained in Production Example 1 was mixed with Aerosil R974 as a filler.
After mixing 20 g (manufactured by Nippon Aerosil), the mixture was uniformly mixed using three paint rolls. In addition, a linear siloxane (containing an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule) and a platinum catalyst (1,1,3,3-tetrafluoroplatinic 1,1,3,3- Methyl-1,3
-Divinyldisiloxane complex) and 1 g of an alkyl acetoacetate aluminum diisopropylate (trade name: Plenact ALM, manufactured by Ajinomoto Fine-Techno) as an organometallic compound were added, and the mixture was sufficiently stirred and mixed to obtain a mixture.
{However, the platinum catalyst is composed of two alkenyl groups of the copolymer [3] such that the chain siloxane has 1.80 times (molar ratio) the SiH groups of the alkenyl groups of the copolymer [3].
It was added so as to be ^10-4 times (molar ratio). ｝

(Example 2) In place of the organometallic compound of Example 1, aluminum monoacetylacetonate bis (ethylacetoacetate) (trade name: aluminum chelate D, manufactured by Kawaken Fine Chemical) was used in the same amount. A mixture was prepared in the same manner as in Example 1. Example 3 A mixture was prepared in the same manner as in Example 1 except that the same amount of dibutyltin dimethoxide was used instead of the organometallic compound of Example 1. (Example 4) Carbon black # 60HN (made by Asahi Carbon) was used instead of Aerosil R974 in Example 1.
A mixture was prepared in the same manner as in Example 1 except that 0 g was used.

(Example 5) In place of the organometallic compound of Example 4, aluminum monoacetylacetonate bis (ethylacetoacetate) (trade name: aluminum chelate D, manufactured by Kawaken Fine Chemical) was used in the same amount. A mixture was prepared in the same manner as in Example 4. Example 6 A mixture was prepared in the same manner as in Example 4 except that the same amount of dibutyltin dimethoxide was used instead of the organometallic compound of Example 4.

Comparative Example 1 A mixture was prepared in the same manner as in Example 1 except that the organometallic compound of Example 1 was not added. Comparative Example 2 A mixture was prepared in the same manner as in Example 4 except that the organometallic compound of Example 4 was not added. (Evaluation) Viscosity of each of the mixtures of Examples 1 to 6 and Comparative Examples 1 and 2 was measured with an E-type viscometer for each of which was sufficiently degassed under reduced pressure [measurement temperature: 23]
° C, EDH 3 °, (28φ) cone used]. The results are shown in Table 1.

[0099]

[Table 1]

From the above results, it was found that by using a small amount of the organometallic compound, the viscosity of the compound could be reduced and the workability was improved. In addition, the compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were poured into
After holding at 30 ° C. for 30 minutes, a cured product having rubber elasticity could be obtained.

[0101]

According to the present invention, the alkenyl group-containing vinyl polymer, the hydrosilyl group-containing compound, the organoaluminum compound and / or the organotitanium compound and / or the organotin compound, and the inorganic filler are used as essential components to increase the viscosity. Thus, a curable composition having reduced and improved workability can be obtained.

Continued on front page F term (reference) 4J002 AC02X BB00X BC00X BD02X BD12X BF01X BG00X BH00X BQ00X CP04W DA036 DE106 DE136 DE236 DG046 DJ016 DJ036 DJ046 EC077 EG047 EZ017 FD016 FD020 FD157 FD200 4J015 CA06 CA07

Claims (18)

[Claims] 1. The following four components: a vinyl polymer (I) containing at least one alkenyl group capable of hydrosilylation in a molecule, a hydrosilyl group-containing compound (II), an organoaluminum compound, an organotitanium compound and A curable composition comprising at least one organometallic compound (III) selected from the group consisting of organotin compounds and an inorganic filler (IV) as an essential component. 2. The curable composition according to claim 1, wherein the molecular weight distribution of the vinyl polymer (I) is less than 1.8. 3. The main chain of the vinyl polymer (I) is (meth)
3. A polymer produced by polymerizing a monomer selected from the group consisting of acrylic acid monomers, nitrile group-containing vinyl monomers, styrene monomers, fluorine-containing vinyl monomers and silicon-containing vinyl monomers. Curable composition. 4. The curable composition according to claim 1, wherein the vinyl polymer (I) is a (meth) acrylic polymer. 5. The curable composition according to claim 1, wherein the vinyl polymer (I) is an acrylic polymer. 6. The curable composition according to claim 1, wherein the vinyl polymer (I) is an acrylate polymer. 7. The curable composition according to claim 1, wherein the main chain of the vinyl polymer (I) is produced by a living radical polymerization method. 8. The curable composition according to claim 7, wherein the living radical polymerization is atom transfer radical polymerization. 9. The method according to claim 7, wherein the atom transfer radical polymerization is carried out in the 7th periodic table.
9. The curable composition according to claim 8, wherein the catalyst is a complex selected from transition metal complexes having a central metal of a Group 8, Group 8, Group 9, Group 10, or Group 11 element. 10. The curable composition according to claim 9, wherein the metal complex used as a catalyst is a complex selected from the group consisting of copper, nickel, ruthenium, and iron complexes. 11. The curable composition according to claim 10, wherein the metal complex used as the catalyst is a copper complex. 12. A vinyl polymer (I) having the terminal structure represented by the general formula (1) by polymerizing a vinyl monomer by an atom transfer radical polymerization method in the following steps: To form an union, -C (R ¹ ) (R ² ) (X) (1) (wherein R ¹ and R ² each represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X is chlorine , Bromine or iodine.) (2) A vinyl polymer obtained by converting a terminal halogen of the polymer into a substituent having an alkenyl group capable of performing a hydrosilylation reaction. The curable composition according to claim 1. 13. A vinyl polymer (I) is produced by the following steps: (1) A vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method;
(2) Subsequently, at least two alkenyl groups having low polymerizability
The curable composition according to any one of claims 1 to 11, wherein the curable composition is a vinyl polymer obtained by reacting a compound having two or more compounds. 14. The curable composition according to claim 1, wherein an alkenyl group capable of undergoing a hydrosilylation reaction is bonded to a terminal of the polymer in the vinyl polymer (I). 15. The hydrosilyl group-containing compound (II) is an organohydrogenpolysiloxane.
15. The curable composition according to any one of items 14 to 14. 16. The curable composition according to claim 1, wherein the organometallic compound (III) is an aluminum chelate compound. 17. An organic metal compound (III) comprising Ti—O
An organic titanium compound having a -C bond.
The curable composition according to any one of items 5 to 5. 18. The curable composition according to claim 1, wherein the organometallic compound (III) is an organotin compound having an alkoxyl group.