JP4865246B2 - Thermal radical curing / thermal cationic curing combined curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition whose viscosity can be maintained low and which can give cured products having excellent heat resistance, weather resistance, oil resistance and the like, having rubber elasticity, and having high mechanical strength. <P>SOLUTION: This curable composition for both thermal radical curing/thermal cation curing, containing the following components (A) and (B) as essential components. (A) A vinylic polymer having two or more groups represented by the general formula (1): -OC(O)C(R<SP>a</SP>)=CH<SB>2</SB>(R<SP>a</SP>is H or a 1 to 20C organic group) in the molecule and having one or more groups represented by the general formula (1) at the molecular ends. (B) An epoxy compound and/or an oxetane compound. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

The present invention relates to a curable composition for thermal radical curing / thermal cation curing. More specifically, the present invention relates to a curable composition for thermal radical curing / thermal cation curing combined use comprising a vinyl polymer having a (meth) acryloyl group at a molecular terminal and an epoxy compound and / or an oxetane compound as essential components.

Acrylic rubber is used as a functional part, a safety part, etc. mainly around the engine of an automobile because of its heat resistance and oil resistance.
However, when the acrylic rubber is cured, the processability such as sticking to the roll at the time of kneading the compounding agent such as filler or vulcanizing agent, difficult to become smooth at the time of sheeting, or non-flowability at the time of molding. There are problems with poor curability, such as poorness and slow vulcanization rate, or the need for long-term post-cure. There are also many problems such as reliability when used as a seal and the necessity of precision machining of the flange surface.
Although what improved processability and curability is also reported (patent document 1), thermosetting which can be fast-cured is possible and productivity cannot be improved.

In order to obtain sufficient rubber elasticity and elongation of the cured product, it is necessary to design a polymer having a large molecular weight between crosslinking points. The present inventors have so far reported a polymer having a main chain as an acrylic polymer obtained by living radical polymerization and having a (meth) acryloyl group at its terminal (Patent Documents 2 and 3).
However, there is a concern that a polymer having a large molecular weight has a high viscosity and is inferior in workability. Further, when a reinforcing filler such as Aerosil is added to an acrylic polymer having insufficient strength, there is a problem that the viscosity is further increased.

Although there have been reports on technologies related to the combined use of thermal radical polymerization and thermal cationic polymerization (Patent Documents 4 and 5), there is no acrylic polymer as the main chain, and heat resistance, weather resistance, and oil resistance. There was no description of balanced materials.
JP 2000-154370 A JP 2000-72816 A JP 2000-95826 A JP 11-29609 A JP 2002-263560 A

An object of this invention is to provide the curable composition which is excellent in heat resistance, weather resistance, oil resistance, etc., is low-viscosity, and is excellent in the intensity | strength characteristic at the time of making it harden | cure.

The present invention relates to a novel curable composition comprising a combination of the following thermal radical curing / thermal cation curing.
(1) A thermal radical curing / thermal cationic curing combined curable composition comprising the following components (A) and (B) as essential components.
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl polymer having two or more groups represented by the formula (1) and one or more groups represented by the general formula (1) at the molecular terminals.
(B) Epoxy compound and / or oxetane compound.
(2) The curable composition according to (1), wherein the vinyl monomer constituting the main chain of the component (A) is a (meth) acrylic monomer.
(3) The curable composition according to any one of (1) to (2), wherein the vinyl monomer constituting the main chain of the component (A) is an acrylate ester monomer.
(4) The vinyl monomer constituting the main chain of the component (A) includes at least two selected from butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. The curable composition as described.

(5) The curable composition according to any one of (1) to (4), wherein R ^a in the general formula (1) of the component (A) is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
(6) The curable composition according to (5), wherein R ^a in the general formula (1) of the component (A) is a hydrogen atom or a methyl group.
(7) The component (A) is
To vinyl polymer having a halogen group at the molecular end,
General formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The curable composition in any one of (1)-(6) manufactured by making the compound shown by react.
(8) A vinyl polymer having a halogen group at the molecular end is represented by the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to an ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
The curable composition as described in (7) which has group shown by these.
(9) Component (A) is
To vinyl polymer having a hydroxyl group at the molecular end,
General formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The curable composition in any one of (1)-(6) manufactured by making the compound shown by react.

(10) The component (A) is
(1) A diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at the molecular end,
(2) Residual isocyanate group and general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The curable composition in any one of (1)-(6) manufactured by making it react with the compound shown by.
(11) The curable composition according to any one of (1) to (10), wherein the main chain of the component (A) is produced by living radical polymerization of a vinyl monomer.
(12) The curable composition according to (11), wherein the living radical polymerization is atom transfer radical polymerization.
(13) The curable composition according to (12), wherein the transition metal complex which is a catalyst for atom transfer radical polymerization is selected from a complex of copper, nickel, ruthenium or iron.
(14) The curable composition according to (13), wherein the transition metal complex is a copper complex.

(15) The curable composition according to any one of (1) to (10), wherein the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent.
(16) The curable composition according to any one of (1) to (15), wherein the number average molecular weight of the component (A) is 3000 or more.
(17) Any of (1) to (16), wherein the vinyl polymer of component (A) has a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is less than 1.8. The curable composition according to 1.
(18) The curable composition according to any one of (1) to (17), which contains a monomer and / or an oligomer having a radical polymerizable group.
(19) The curable composition according to any one of (1) to (18), which contains a monomer and / or an oligomer having an anionically polymerizable group.

(20) The curable composition according to any one of (18) to (19), which contains a monomer and / or an oligomer having a (meth) acryloyl group.
(21) The curable composition according to (20), comprising a monomer and / or an oligomer having a (meth) acryloyl group and having a number average molecular weight of 5000 or less.
(22) The curable composition according to any one of (1) to (21), wherein the epoxy compound and oxetane compound of component (B) do not have an aromatic ring.
(23) The curable composition according to any one of (1) to (22), wherein the epoxy compound and oxetane compound of component (B) have an alicyclic structure.
(24) The curable composition according to any one of (1) to (23), which contains (C) a thermal radical polymerization initiator in addition to the components (A) and (B).

(25) The curable composition according to (24), further comprising a redox initiator.
(26) The curable composition according to any one of (1) to (25), which contains (D) a heat-cleavable cationic polymerization initiator in addition to the components (A) and (B).
(27) In addition to the components (A) and (B), any one of (1) to (23) containing (C) a thermal radical polymerization initiator and (D) a heat-cleavable cationic polymerization initiator The curable composition according to 1.
(28) The curable composition according to any one of (1) to (27), further comprising (E) a compound having both an epoxy group and a (meth) acryloyl group in the molecule.
(29) The curable composition according to (28), wherein the component (E) is glycidyl methacrylate.

The curable composition for thermal radical curing / thermal cation curing combined use of the present invention is described below.
The curable composition of the present invention is a thermal radical curing / thermal cation curing combined curable composition comprising the following components (A) and (B) as essential components.
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl polymer having two or more groups represented by the formula (1) and one or more groups represented by the general formula (1) at the molecular terminals.
(B) Epoxy compound and / or oxetane compound.

<< (A) component >>
The component (A) is represented by the general formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Is a vinyl polymer having two or more groups represented by general formula (1) and one or more groups represented by the general formula (1) at the molecular terminals.

The number of groups ((meth) acryloyl group) represented by the above general formula (1) in the component (A) is 2 or more per molecule, and 1 or more at the molecular end. Two per molecule are preferred.
Since the side reaction may actually occur when the component (A) is produced, the average value of the number of the (meth) acryloyl groups in the produced vinyl polymer mixture is less than 2. May be. In the present invention, when the average value of the number of (meth) acryloyl groups in the actually produced vinyl polymer mixture is 1.1 or more, this mixture is referred to as component (A). That is, the component (A) includes a mixture of vinyl polymers containing a vinyl polymer having two or more (meth) acryloyl groups per molecule and one or more molecules per molecule.
From the viewpoint of crosslinking, the average value of the number of the (meth) acryloyl group is preferably 1.5 or more per molecule.
Furthermore, one or more of the (meth) acryloyl group is present at the molecular end, but the position of the other (meth) acryloyl group is not particularly limited. From the viewpoint that the distance between cross-linking points can be increased, a form close to the other molecular end is preferable, and a form close to the other molecular end is particularly preferable.

R ^a in the (meth) acryloyl group represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a nitrile group, and the like. And the like.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.
Preferred examples of R ^a include, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), —C ₆ H ₅ , — CH ₂ OH, —CN and the like can be mentioned, and preferably —H, —CH ₃ .

(A) There is no limitation in particular as a vinyl-type monomer which comprises the principal chain of a component, A various thing can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2- Perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid diper Fluoromethylmethyl, (meth) acrylic acid 2-perf (Meth) such as fluoromethyl-2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Acrylic monomers; aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and their salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; vinyl Silicon-containing vinyl monomers such as trimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; Maleimide monomers such as reimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile Amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene, isoprene, etc. And conjugated dienes such as vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or in combination.

Of these, aromatic vinyl monomers and (meth) acrylic monomers are preferred from the viewpoint of physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, and more preferred are butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. Furthermore, from the viewpoint of oil resistance and the like, it is particularly preferable that the vinyl monomer constituting the main chain includes at least two selected from butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate.

In the present invention, these preferable monomers may be copolymerized with the other monomers, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40% or more. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

The molecular weight distribution of the component (A) [the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC)] is not particularly limited, but is preferably less than 1.8. More preferably, it is 1.7 or less, more preferably 1.6 or less, particularly preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.
In the GPC measurement in the present invention, usually, chloroform or tetrahydrofuran is used as a mobile phase, a polystyrene gel column is used, and the molecular weight value is obtained in terms of polystyrene.

The lower limit of the number average molecular weight of the component (A) is preferably 500, more preferably 3000, and the upper limit is preferably 100,000, more preferably 40000. If the molecular weight is less than 500, the original characteristics of the vinyl polymer tend to be hardly expressed, and if it exceeds 100,000, handling tends to be difficult.

<Production method of component (A)>
There is no limitation in particular about the manufacturing method of (A) component.
The vinyl polymer is generally produced by anionic polymerization or radical polymerization, but radical polymerization is preferred because of the versatility of the monomer or ease of control. Among radical polymerizations, it is preferably produced by living radical polymerization or radical polymerization using a chain transfer agent, and the former is particularly preferable.

The radical polymerization method used for the production of the component (A) is a method in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound, a peroxide or the like as a polymerization initiator. Can be classified into “radical polymerization method” and “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position such as a terminal.

The “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount. On the contrary, if the monomer is used in a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced increases. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

The “controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, and a polymerization growth terminal. Can be classified as a “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing without causing a termination reaction or the like.

In the “chain transfer agent method”, a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and high viscosity can be obtained because of free radical polymerization.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
Therefore, in the “living radical polymerization method”, a polymer having a narrow molecular weight distribution and a low viscosity can be obtained, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The production method of the vinyl polymer having the specific functional group is more preferable.

Living polymerisation means, in a narrow sense, polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. Pseudo-living polymerization in which is grown while in equilibrium. The definition in the present invention is also the latter.

The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in Journal of the American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules, 1994, Vol. 27, page 7228, using radical scavengers such as nitroxide compounds, organic halides etc. as initiators and transition metal complexes as catalysts. Atom transfer radical polymerization (ATRP) etc. are mentioned.

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers 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 of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the production of vinyl polymers having specific functional groups The method is more preferable.

Examples of the atom transfer radical polymerization method include, for example, Matyjazewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules. 1995, 28, 7901, Science 1996, 272, 866, WO 96/30421 pamphlet, WO 97/18247 pamphlet or Sawamoto et al., Macromolecules 1995, 28, The method described in page 1721 etc. is mentioned.

In the present invention, there is no particular restriction as to which of these methods is used, but basically, a controlled radical polymerization method is used, and a living radical polymerization method is preferred from the viewpoint of ease of control, and particularly an atom transfer radical. A polymerization method is preferred.

First, one of the controlled radical polymerization methods, a polymerization method using a chain transfer agent will be described.
The radical polymerization using a chain transfer agent (telomer) is not particularly limited, but the following two methods are exemplified as a method for obtaining a vinyl polymer having a terminal structure suitable for the present invention.
JP-A-4-132706 discloses a method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method for obtaining a hydroxyl-terminated polymer by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

Next, the living radical polymerization method will be described.
First, a method using a radical scavenger (capping agent) such as a nitroxide compound will be described.
In this polymerization method, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Such compounds are not particularly limited, but are cyclic such as 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical. Nitroxy free radicals from hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable.

Specific examples of the nitroxy free radical compound 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, Examples include 1,1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like.
Instead of the nitroxy free radical, a stable free radical such as a 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.
Although the combined ratio of both is not particularly limited, 0.1 to 10 mol of the radical initiator is appropriate 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 the polymerization temperature condition is preferable.
The peroxide is not particularly limited, but diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, bis Examples include peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctate, and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable.
Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

As reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and a radical generator together, the following alkoxyamine compound may be used as an initiator. I do not care.

When an alkoxyamine compound is used as an initiator, if it has a functional group such as a hydroxyl group as described above, a polymer having a functional group at the terminal can be obtained. When this is used in the present invention, a polymer having a functional group at the terminal is obtained.

There are no particular limitations on the polymerization conditions such as the monomer, solvent, and polymerization temperature used in the polymerization using a radical scavenger such as the nitroxide compound, but it may be the same as that used for the atom transfer radical polymerization described below.

Next, a more preferred atom transfer radical polymerization method will be described as the living radical polymerization method used in the present invention.
In this atom transfer radical polymerization method, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having halogen at the α-position or a compound having halogen at the benzyl-position), or halogen A sulfonyl chloride compound or the like is used as an initiator.

For example,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2
(Wherein C ₆ H ₅ is a phenyl group, X is a chlorine atom, a bromine atom or an iodine atom),
^{_{R 3 -C (H) (X}} ) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C (H) (X) -C (O) R 4 _{^{, R 3 -C (CH 3)}} (X) -C (O) R 4
(Wherein R ³ and R ⁴ are a hydrogen atom, 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, X is a chlorine atom, bromine atom or iodine atom) ),
R ³ —C ₆ H ₄ —SO ₂ X
(Wherein R ³ is a hydrogen atom, 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, X is a chlorine atom, bromine atom or iodine atom)
Etc.

As an initiator of the atom transfer radical polymerization method, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a structure represented by the general formula (1) at the end of one main chain and the functional group at the other main chain end is produced.
Examples of the 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 the alkenyl group is not particularly limited, and for example, the general formula (6):
^{R 6 R 7 C (X)} -R 8 -R 9 -C (R 5) = CH 2 (6)
(In the formula, R ⁵ is a hydrogen atom or a methyl group, R ⁶ and R ⁷ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or others. R ⁸ is —C (O) O— (ester group), —C (O) — (keto group) or o-, m-, p-phenylene group, R ⁹ is a direct bond Or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds, X is a chlorine atom, a bromine atom or an iodine atom)
What is shown by is illustrated.

Specific examples of the substituents R ⁶ and R ⁷ include a hydrogen atom, a methyl group, 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.
Examples of the divalent organic group having 1 to 20 carbon atoms that may contain one or more ether bonds of R ⁹ include, for example, 1 to 20 carbon atoms that may contain one or more ether bonds. An alkylene group etc. are mentioned.

Specific examples of the organic halide having an alkenyl group represented by the general formula (6) include
_{XCH 2 C (O) O (} CH 2) n CH = CH 2,
H ₃ CC (H) (X) C (O) O (CH ₂ ) _n CH═CH ₂ ,
(H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n CH═CH ₂ ,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n CH = CH 2,

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20),
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2
(In the above formulas, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20)
Etc.

The organic halide having an alkenyl group is further represented by the general formula (7):
_{^{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (7)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group) ) Or o-, m-, p-phenylene group)
The compound shown by these is mentioned.

R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), and in the case of a direct bond, a halogen atom is bonded. A vinyl group is bonded to the carbon, and is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group, a phenylene group or the like as R ¹⁰ , and a direct bond may be used. When R ⁹ is not a direct bond, R ¹⁰ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

If the compound represented by the general formula (7) is specifically exemplified,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X,
_{CH 2 = CHC (H) (} X) CH 3, CH 2 = C (CH 3) C (H) (X) CH 3,
_{CH 2 = CHC (X) (} CH 3) 2, CH 2 = CHC (H) (X) C 2 H 5,
_{CH 2 = CHC (H) (} X) CH (CH 3) 2,
_{CH 2 = CHC (H) (} X) C 6 H 5, CH 2 = CHC (H) (X) CH 2 C 6 H 5,
_{CH 2 = CHCH 2 C (H} ) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 8 C (H) (X) -CO 2 R,
_{CH 2 = CHCH 2 C (H} ) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -C 6 H 5
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

Specific examples of the sulfonyl halide compound having the alkenyl group include
_{o-, m-, p-CH 2} = CH- (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 the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
Etc.

The organic halide having a crosslinkable silyl group is not particularly limited. For example, the general formula (8):
^{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 (8)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X are the same as above, R ¹¹ , R ¹² are all alkyl groups, aryl groups, aralkyl groups having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). An organosiloxy group, 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 Y is two or more When present, they may be the same or different, a is 0, 1, 2 or 3, b is 0, 1 or 2, m is an integer from 0 to 19, provided that a + mb ≧ 1 Satisfy)
The following are exemplified.

If the compound represented by the general formula (8) is specifically exemplified,
XCH ₂ C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (OCH 3) 3,
(CH ₃ ) ₂ C (X) C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{XCH 2 C (O) O (} CH 2) n Si (CH 3) (OCH 3) 2,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
_{(CH 3) 2 C (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
(In the above formula, X is a chlorine atom, bromine atom, iodine atom, n is an integer of 0-20),
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (CH 3) (OCH 3) 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2
(Wherein X is a chlorine atom, bromine atom, iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3
(In the above formula, X is a chlorine atom, a bromine atom or an iodine atom)
Etc.

The organic halide having a crosslinkable silyl group is further represented by the general formula (9):
_{^{(R 12) 3-a (}} Y) a Si- [OSi (R 11) 2-b (Y) b] m -CH 2 -C (H) (R 5) -R 9 -C (R 6) ( X) -R ¹⁰ -R ⁷ (9)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , a, b, X, Y are the same as above, m is an integer of 0-19)
What is shown by is illustrated.

If the compound represented by the general formula (9) is specifically exemplified,
_{(CH 3 O) 3 SiCH 2} CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -C 6 H 5,
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said hydroxyl group, The following are illustrated.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, R is 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)

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said amino group, The following are illustrated.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, R is 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)

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said epoxy group, The following are illustrated.

(Wherein X is a chlorine atom, bromine atom or iodine atom, R is 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)

In order to obtain a vinyl polymer having two or more groups represented by the general formula (1) per molecule at the molecular end, an organic halide or sulfonyl halide compound having two or more starting points is used as an initiator. It is preferable to use as. For example,

Etc.
There is no restriction | limiting in particular in the vinyl-type monomer used in this superposition | polymerization, and all already illustrated can be used suitably.

Further, the transition metal complex used as a polymerization catalyst is not particularly limited, but preferably a metal complex having a central metal of Group 7, Group 8, Group 9, Group 11 or Group 11 of the periodic table, for example, copper, It is a metal complex of nickel, ruthenium and iron. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable.

Specific examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. Is mentioned.
When a copper compound is used, 2,2′-bipyridyl, its derivative, 1,10-phenanthroline, its derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as polyamine can be added.

A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst.
When a ruthenium compound is used as a catalyst, aluminum alkoxides can be added as an activator.
Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistributylphosphine complex ( NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The polymerization can be carried out without solvent or in various solvents.
Solvent types include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more.
Moreover, superposition | polymerization can be performed in room temperature-200 degreeC, Preferably it is 50-150 degreeC.

<Functional group introduction method>
(A) Although the manufacturing method of component is not particularly limited, for example, a vinyl polymer having a reactive functional group is manufactured by the above-described method, and the reactive functional group is changed to a substituent having a (meth) acryloyl group. It can be manufactured by converting.
Below, the method to convert the terminal of the vinyl polymer which has a reactive functional group into group represented by General formula (1) is demonstrated.

The method for introducing the (meth) acryloyl group at the terminal of the vinyl polymer is not particularly limited, and examples thereof include the following methods.
(Introduction method 1) A vinyl polymer having a halogen group (halogen atom) at the terminal, and the general formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The method by reaction with the compound shown by these.
As a vinyl polymer having a halogen group at the terminal, the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to an ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
Those having a terminal group represented by are preferred.

(Introduction method 2) A vinyl polymer having a hydroxyl group at the terminal, and the general formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The method by reaction with the compound shown by these.
(Introduction method 3) A vinyl polymer having a hydroxyl group at the terminal is reacted with a diisocyanate compound to form a residual isocyanate group and the general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The method by reaction with the compound shown by these.

Below, each said method is demonstrated in detail.
[Introduction method 1]
The introduction method 1 is a method by a reaction between a vinyl polymer having a halogen group at the terminal and a compound represented by the general formula (2).
The vinyl polymer having a halogen group at the terminal is not particularly limited, but a vinyl polymer having a terminal group represented by the general formula (3) is preferable.
Examples of the group bonded to the ethylenically unsaturated group of the vinyl monomer in R ¹ and R ² in the general formula (3) include a hydrogen atom, a methyl group, a carbonyl group, a carboxylate group, a toluyl group, a fluoro group, and a chloro group. , Trialkoxysilyl group, phenylsulfonic acid group, carboxylic acid imide group, cyano group and the like.
A vinyl polymer having a halogen group at the terminal, particularly a vinyl polymer having a terminal group represented by the general formula (3), is prepared by using the above-described organic halide or sulfonyl halide compound as an initiator and catalyzing a transition metal complex. Is produced by a method of polymerizing a vinyl monomer or a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, but the former is preferred.

There is no limitation in particular in the compound represented by General formula (2).
Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (2) are the same as those described above, and specific examples thereof are the same as those described above.
M ⁺ in the general formula (2) is a counter cation of an oxyanion, and examples of the type include alkali metal ions and quaternary ammonium ions.

Examples of the alkali metal ions include lithium ions, sodium ions, and potassium ions.
Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, dimethylpiperidinium ion, and the like.
Of these, alkali metal ions are preferable, and sodium ions and potassium ions are more preferable.

The usage-amount of the compound shown by General formula (2) becomes like this. Preferably it is 1-5 equivalent with respect to the terminal group shown by General formula (3), More preferably, it is 1.0-1.2 equivalent.
The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 2]
The introduction method 2 is a method by a reaction between a vinyl polymer having a hydroxyl group at the terminal and a compound represented by the general formula (4).
There is no limitation in particular in the compound represented by General formula (4).
Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (4) are the same as those described above, and specific examples thereof are the same as those described above.

The vinyl polymer having a hydroxyl group at the terminal is a method of polymerizing a vinyl monomer using the above-mentioned organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a compound having a hydroxyl group as a chain transfer agent. Is produced by a method of polymerizing a vinyl monomer, but the former is preferred.

Although there is no limitation in particular in the method of manufacturing the vinyl polymer which has a hydroxyl group at the terminal, For example, the following methods are illustrated.
(A) When synthesizing a vinyl polymer by living radical polymerization, the general formula (10):
_{^{H 2 C = C (R 13}} ) -R 14 -R 15 -OH (10)
(In the formula, R ¹³ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ¹⁴ is —C (O) O— (ester group) or o-, m- or p-phenylene group, and R ¹⁵ is a direct bond. Or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds)
A method of reacting a compound having a polymerizable alkenyl group and a hydroxyl group in one molecule as a second monomer.

R ¹³ is preferably a hydrogen atom or a methyl group. Further, when R ¹⁴ is an ester group, it is a (meth) acrylate compound, and when R ¹⁴ is a phenylene group, it is a styrene compound. A specific example of R ¹⁵ is the same as the specific example of R ⁹ .
There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule, but the end of the polymerization reaction or the completion of the reaction of a predetermined monomer is particularly desired when rubber-like properties are expected. Later, it is preferable to react as the second monomer.

(B) When synthesizing a vinyl polymer by living radical polymerization, it has a low polymerizable alkenyl group and hydroxyl group in the molecule as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined monomer. A method of reacting a compound.
Although there is no limitation in particular in the said compound, For example, General formula (11):
_{^{H 2 C = C (R 13}} ) -R 16 -OH (11)
(In the formula, R ¹³ is the same as described above, and R ¹⁶ represents a C 1-20 divalent organic group optionally having one or more ether bonds)
And the like.
A specific example of R ¹⁶ is the same as the specific example of R ⁹ .

Although there is no limitation in particular in the compound shown by General formula (11), The alkenyl alcohol like 10-undecenol, 5-hexenol, and allyl alcohol is preferable from the point that acquisition is easy.

(C) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization by a method as disclosed in JP-A-4-132706. A method of introducing a hydroxyl group at a terminal by hydrolysis or reaction with a hydroxyl group-containing compound.

(D) To a vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization, the general formula (12):
^{M + C - (R 17)} (R 18) -R 16 -OH (12)
(In the formula, R ¹⁶ and M ⁺ are the same as described above, and R ¹⁷ and R ¹⁸ are both an electron-withdrawing group for stabilizing carbanion C ⁻ or one is the electron-withdrawing group, the other is a hydrogen atom, and 1 to 10 carbon atoms. Represents an alkyl group or a phenyl group)
A method in which a halogen atom is substituted by reacting a stabilized carbanion having a hydroxyl group represented by formula (1).

Examples of the electron withdrawing group include —CO ₂ R (ester group), —C (O) R (keto group), —CON (R ₂ ) (amide group), —COSR (thioester group), —CN (nitrile group). ), —NO ₂ (nitro group) and the like, and —CO ₂ R, —C (O) R, and —CN are particularly preferable. 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 an alkyl group having 1 to 10 carbon atoms or a phenyl group.

(E) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization is allowed to react with a metal simple substance or an organometallic compound such as zinc to enolate. A method in which an anion is prepared and then an aldehyde or a ketone is reacted.

(F) A vinyl polymer having at least one halogen atom represented by the general formula (3), preferably a halogen atom at the terminal of the polymer, is represented by the general formula (13):
HO-R ^{< 16 >} -O ^- M ^<+> (13)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A hydroxyl group-containing compound represented by the general formula (14):
HO—R ¹⁶ —C (O) O ⁻ M ⁺ (14)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A method in which the halogen atom is substituted with a hydroxyl group-containing substituent by reacting the hydroxyl group-containing compound represented by formula (1).

In the case where a halogen atom is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), the method of (b) is more preferred because control is easier.
In addition, when a hydroxyl group is introduced by converting a halogen atom of a vinyl polymer having at least one carbon-halogen bond such as (c) to (f), control is easier (f). The method is more preferable.

The usage-amount of the compound shown by General formula (4) becomes like this. Preferably it is 1-10 equivalent with respect to the terminal hydroxyl group of a vinyl type polymer, More preferably, it is 1-5 equivalent.
The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. Amides, acetonitrile and the like are preferably used.
Although reaction temperature does not have limitation in particular, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 3]
In the introduction method 3, a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at the terminal, and the residual isocyanate group and the general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ′ represents a divalent organic group having 2 to 20 carbon atoms)
It is the method by reaction with the compound shown by.

Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (5) are the same as those described above, and specific examples thereof are the same as those described above.
Examples of the divalent organic group having 2 to 20 carbon atoms represented by R ′ in the general formula (5) include an alkylene group having 2 to 20 carbon atoms (ethylene group, propylene group, butylene group, etc.), and 6 to 20 carbon atoms. And an arylene group having 7 to 20 carbon atoms.
Although there is no limitation in particular in the compound shown by General formula (5), As a particularly preferable compound, 2-hydroxypropyl methacrylate etc. are mentioned.
The vinyl polymer having a hydroxyl group at the terminal is as described above.

There is no particular limitation on the diisocyanate compound, and any conventionally known one can be used. Specific examples include toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogen. Xylylene diisocyanate, isophorone diisocyanate and the like. These may be used alone or in combination of two or more. Moreover, you may use block isocyanate. From the viewpoint of obtaining better weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

The amount of the diisocyanate compound used is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, with respect to the terminal hydroxyl group of the vinyl polymer.
The usage-amount of the compound shown by General formula (5) becomes like this. Preferably it is 1-10 equivalent with respect to a residual isocyanate group, More preferably, it is 1-5 equivalent.
The reaction solvent is not particularly limited, but an aprotic solvent is preferred.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-250 degreeC, More preferably, it is 20-200 degreeC.

<< (B) component >>
In the curable composition of the present invention, an epoxy compound and / or an oxetane compound is used as the component (B).

The epoxy compound (B) serves to lower the viscosity of the component (A), improve workability, and increase the strength of the cured product.
The epoxy compound may be any compound as long as it has an epoxy group, and examples thereof include bisphenol type epoxy resins and alicyclic epoxy resins.
Moreover, the following epoxy compounds may be used independently or may use 2 or more types together.

Specific examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, and the like. It is done.
The hydrogenated type refers to a product obtained by hydrogen reduction of a benzene ring part to a cyclohexyl ring.

Typical examples of the alicyclic epoxy resins include compounds having a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, and the like. Specifically, vinylcyclohexene diepoxide, vinylcyclohexene monoepoxide, 3,4- Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3 , 4-epoxycyclohexyl) adipate, bis (3,4-epoxycyclohexylmethyl) adipate, and the like.

The oxetane compound as the component (B) serves to lower the viscosity of the component (A), improve workability, and increase the strength of the cured product.
The oxetane compound is not particularly limited, and specific examples include 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, and (3-ethyl-3-oxetanylmethoxy) methyl. Benzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3- Ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl- 3-Oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl- -Oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) Ether, dicyclopentenylethyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2- Tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxeta) Rumethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, Pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis (3- Oxetanyl) -5-oxa-nonane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl Propane], ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl-3-oxetanylmethyl) ether Tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylenebis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis [(3-ethyl-3-oxetanyl) Methoxy) methyl] butane, 1,6-bis [(3-ethyl-3-oxetanylmethoxy) methyl] hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl -3-Oxetanylmethi ) Ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl) -3-oxetanylmethyl) ether, EO-modified bisphenol F bis (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris (3-ethyl-3) -Oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis 3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether and the like.
The oxetane compounds may be used alone or in combination of two or more.

The epoxy compound and oxetane compound preferably have no aromatic ring. Moreover, what has an alicyclic structure is preferable.

(B) As usage-amount of a component, 10-200 parts are preferable with respect to 100 weight part (henceforth part) of (A) component, and 20-150 parts are more preferable. When the amount of the component (B) used is less than 10 parts, the effect of improving the strength tends to be insufficient, and when it exceeds 200 parts, the elongation tends to be insufficient.

<< (C) component >>
The thermal radical polymerization initiator of component (C) can be further used to thermally cure component (A).
(C) Although it does not specifically limit as a thermal radical polymerization initiator of a component, An azo initiator, a peroxide initiator, a persulfate initiator, etc. are mentioned.

Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2'-azobis (2- Amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis (isobutyronitrile) (VAZO 64), 2, 2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,2'-azobis (2- Cyclopropylpropionitrile), and 2,2′-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries, Ltd.) And the like.

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl). Peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl per Oxy-2-ethylhexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.
Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, and the like.

The said initiator may be used independently or may use 2 or more types together.
Of the above thermal radical polymerization initiators, those selected from the group consisting of azo initiators and peroxide initiators are preferred. More preferred are 2,2'-azobis (methyl isobutyrate), benzoyl peroxide, t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof. .

In addition to the thermal radical polymerization initiator, a redox initiator can be further used in combination.
Suitable redox initiators include, but are not limited to, combinations of the above persulfate initiators and reducing agents (sodium metabisulfite, sodium bisulfite, etc.); Combinations of tertiary amines such as benzoyl peroxide and dimethylaniline, cumene hydroperoxides and anilines; organic peroxides and transition metals such as cumene hydroperoxide and cobalt naphthate It is done. Preferred is a combination of an organic peroxide and a tertiary amine, a combination of an organic peroxide and a transition metal, more preferably a combination of cumene hydroperoxide and anilines, cumene hydroperoxide and cobalt naphthate. It is a combination.
Other initiators can also be used. Examples of other initiators include, but are not limited to, pinacol such as tetraphenyl 1,1,2,2-ethanediol.

The thermal radical polymerization initiator used in the present invention is present in a catalytically effective amount, and although such amount is not limited, it can typically be added to the component (A) of the present invention and others. When the total amount of the monomer and / or oligomer mixture described below is 100 parts, it is preferably about 0.01 to 3 parts, more preferably about 0.025 to 2 parts. In addition, when the mixture of initiators is used, it is preferable that the total amount of the mixture of initiators exists in the said range.

<< (D) component >>
The heat-cleavable cationic polymerization initiator of the component (D) can be further used to induce ring opening of the epoxy compound and / or oxetane compound of the component (B).
In addition, as the heat-cleavable cationic polymerization initiator, any compound that can induce the opening of an epoxy group or an oxetane ring by heating can be used.

Specific examples of the thermal cleavage type cationic polymerization initiator include quaternary ammonium salts, tertiary amine salts, phosphonium salts, sulfonium salts, diazonium salts, iodonium salts and the like.
Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, and the like.

Examples of the tertiary amine salt include N, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-dimethyl-N-benzylaniline. Nitrotetrafluoroborate, N, N-diethyl-N-benzyltrifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl-N- (4-methoxy Benzyl) toluidinium hexafluoroantimonate and the like.
Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsinate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, diphenyl (4-phenylthiophenyl). ) Sulfonium hexafluoroarsinate, 2-butenyltetramethylenesulfonium hexafluoroantimonate, and the like. The products that can be used include Optomer SP150, Optomer SP170, Optomer SP172, Adeka Opton CP-66, Adeka Opton CP-77, Sanade Chemical SI-80L, Sun Aid SI-manufactured by Sanshin Chemical Co., Ltd. 100L, CYRACURE UVI-6974 manufactured by Union Carbide Co., Ltd., UVI-6990, UVI-508, UVI-509 manufactured by CYRACURE General Electric Co., Ltd., FC- manufactured by Minnesota Mining and Manufacturing Co., Ltd. 508, FC-509, CD-1010, CD-1011 manufactured by Thursmer Co., Ltd. and the like.

Examples of the diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate. Examples of products that can be used include AMERICURE manufactured by American Canon Inc., ULTRASET manufactured by Asahi Denka Co., Ltd., and the like.

Examples of the iodonium salt include diphenyl iodonium hexafluoroarsinate, bis (4-chlorophenyl) iodonium hexafluoroarsinate, bis (4-bromophenyl) iodonium hexafluoroarsinate, phenyl (4-methoxyphenyl) iodonium hexafluoroarsinate. And the like. Examples of products that can be used include UV-9310C manufactured by Toshiba Silicone Co., Ltd., Photoinitiator 2074 manufactured by Rhone-Poulenc Co., Ltd., UVE series products manufactured by General Electric Co., Ltd., and Minosota Mining and Manufacturing Co., Ltd. Examples include the FC series made by the manufacturer.

The said initiator may be used independently or may use 2 or more types together.
Of the above thermal cleavage type cationic polymerization initiators, sulfonium salts are preferred.

Although there is no restriction | limiting in particular as the usage-amount of a heat-cleavage type cationic polymerization initiator, It is 0.1-15 parts from a sclerosing | hardenable point with respect to 100 parts of epoxy compounds and / or oxetane compounds of (B) component. In view of balance of physical properties of the cured product, it is more preferably 0.3 to 8.0 parts.

<< (E) component >>
The compound having both an epoxy group and a (meth) acryloyl group in the component (E) molecule crosses the (A) component and the (B) component for the purpose of further improving the mechanical strength and elongation as necessary. It can be used as a linking compound.
The component (E) is not particularly limited as long as it is a compound having both an epoxy group and a (meth) acryloyl group in the molecule, but glycidyl methacrylate is preferable from the viewpoint of availability.
(E) As usage-amount of a component, 0.1-30 parts are preferable with respect to a total of 100 parts of (A) component and (B) component, and 0.5-20 parts are more preferable.

<< Curable composition >>
The curable composition of the present invention is a thermal radical curing / thermal cation curing combined curing composition comprising the component (A) and the component (B) as essential components as described above. Moreover, (C), (D), (E) component can be contained as needed.
Furthermore, a polymerizable monomer and / or oligomer can be used in combination for the purpose of improving surface curability, imparting toughness, and improving workability by reducing viscosity.

<Polymerizable monomer and / or oligomer>
As the polymerizable monomer and / or oligomer, a monomer and / or oligomer having a radical polymerizable group or a monomer and / or oligomer having an anion polymerizable group is preferable from the viewpoint of curability.

Examples of the radical polymerizable group include (meth) acryloyl group such as (meth) acryl group, styrene group, acrylonitrile group, vinyl ester group, N-vinylpyrrolidone group, acrylamide group, conjugated diene group, vinyl ketone group, and chloride. A vinyl group etc. are mentioned. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.

Examples of the anionic polymerizable group include a (meth) acryloyl group such as a (meth) acryl group, a styrene group, an acrylonitrile group, an N-vinylpyrrolidone group, an acrylamide group, a conjugated diene group, and a vinyl ketone group. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.

Specific examples of the monomer include (meth) acrylate monomers, cyclic acrylates, styrene monomers, acrylonitrile, vinyl ester monomers, N-vinyl pyrrolidone, acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, vinyl halides. -A vinylidene halide monomer, a polyfunctional monomer, etc. are mentioned.

(Meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth ) N-octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate , Phenyl (meth) acrylate, toluyl (meth) acrylate, (meth) acrylic Benzyl, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylic acid glycidyl, (meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethylmethyl, (meta ) 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate , Perfluoromethyl (meth) acrylate, (meth) Diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, Examples include (meth) acrylic acid 2-perfluorohexadecylethyl. Moreover, the compound etc. which are shown by the following Formula can also be mention | raise | lifted. In the following formula, n represents an integer of 0-20.

Examples of the styrenic monomer include styrene and α-methylstyrene.
Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl butyrate.
Examples of the acrylamide monomer include acrylamide and N, N-dimethylacrylamide.
Examples of the conjugated diene monomer include butadiene and isoprene.
Examples of the vinyl ketone monomer include methyl vinyl ketone.
Examples of the vinyl halide / vinylidene halide monomer include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.

Multifunctional monomers include trimethylolpropane triacrylate, neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, dipentaerythritol polyhexanolide hexa Chlorate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1 , 3-dioxane, tetrabromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetra Chi glycol diacrylate, 1,9-nonanediol diacrylate, and ditrimethylolpropane tetraacrylate.

As the oligomer, epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolac type epoxy acrylate resin, cresol novolac type epoxy acrylate resin, COOH group-modified epoxy acrylate type resin; polyol (polytetramethylene glycol, ethylene glycol and adipine) Acid polyester diol, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanate (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane) Diisocyanate, hexamethylene diisocyanate A urethane resin obtained from a hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.)} Urethane acrylate resin obtained by reaction; resin in which a (meth) acryl group is introduced into the polyol via an ester bond; polyester acrylate resin, poly (meth) acryl acrylate resin (having a polymerizable reactive group) Poly (meth) acrylic ester resin) and the like.

Of the above, monomers and / or oligomers having a (meth) acryloyl group are preferred. The number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is preferably 5000 or less. Furthermore, in the case of using a monomer for improving the surface curability and reducing the viscosity for improving workability, it is more preferable that the molecular weight is 1000 or less because of good compatibility.

As the use amount of the polymerizable monomer and / or oligomer, from the viewpoint of workability by improving surface curability, imparting toughness, and reducing viscosity, the total of 100 parts of the component (A) and the component (B), 1 to 200 parts are preferable, and 5 to 100 parts are more preferable.

<Various additives>
Various additives and the like may be blended with the curable composition of the present invention in order to adjust physical properties.

<Solvent>
An organic solvent may be added to the curable composition of the present invention from the viewpoint of workability during coating, drying before and after curing, and the like.
As the organic solvent, those having a boiling point of 50 to 180 ° C. are usually preferable because of excellent workability during coating and drying before and after curing. Specifically, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, etc. Ester solvents; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; and cyclic ether solvents such as dioxane. These solvents may be used alone or in combination of two or more.
The amount of the solvent used is preferably 1 to 900 parts with respect to a total of 100 parts of the component (A) and the component (B) from the viewpoint of the balance of the finished product, workability, and drying.

<Reinforcing silica>
Reinforcing silica may be added to the curable composition of the present invention from the viewpoint of improving the strength of the cured product.
Examples of the reinforcing silica include fumed silica and precipitated silica. Among these, those having a particle diameter of 50 μm or less and a specific surface area of 80 m ² / g or more are preferable from the viewpoint of reinforcing effect. In addition, the measuring method of a specific surface area is as the below-mentioned.

Further, surface-treated silica such as organosilane, organosilazane, diorganocyclopolysiloxane and the like is more preferable because it easily exhibits fluidity suitable for molding.
As a more specific example of the reinforcing silica, there is no particular limitation. However, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Industry Co., Ltd., which is one of precipitated silicas. Nipsil etc. are mentioned.

The reinforcing silica may be used alone or in combination of two or more.
Although there is no restriction | limiting in particular in the addition amount of a reinforcing silica, Preferably it is 0.1-100 parts with respect to a total of 100 parts of the said (A) component and (B) component, More preferably, it is 0.5-80 parts. More preferably, it is 1 to 50 parts. When the amount is less than 0.1 part, the effect of improving the reinforcing property may not be sufficient, and when it exceeds 100 parts, the workability of the curable composition may be deteriorated.

<Filler>
In the curable composition of the present invention, various fillers may be used as necessary in addition to the reinforcing silica.
The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, dolomite, silicic anhydride, Reinforcing fillers such as hydrous silicic acid and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, bengara, Fillers such as fine aluminum powder, flint powder, zinc oxide, activated zinc white, zinc powder, zinc carbonate and shirasu balloon; fibrous fillers such as asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber, etc. Is mentioned. Of these fillers, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. In addition, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. may be added. it can.

In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product. Moreover, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When the surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved as compared with the case where calcium carbonate that is not surface-treated is used, and the adhesiveness and weather resistance of the curable composition are improved. The improvement effect is considered to be further improved.

As the surface treatment agent, organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents are used. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc. And sodium salts and potassium salts of these fatty acids, and alkyl esters of these fatty acids.
Specific examples of surfactants include sodium anion surfactants such as polyoxyethylene alkyl ether sulfates and long-chain alcohol sulfates, sulfate-type anionic surfactants such as potassium salts, alkylbenzene sulfonic acids, alkylnaphthalene sulfonic acids, paraffins Examples thereof include sulfonic acid type anionic surfactants such as sodium salts and potassium salts such as sulfonic acid, α-olefin sulfonic acid and alkylsulfosuccinic acid.

The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight (hereinafter referred to as “%”) with respect to calcium carbonate, and more preferably in the range of 1 to 5%. When the treatment amount is less than 0.1%, the workability, adhesiveness and weatherability adhesion may not be sufficiently improved. When the treatment amount exceeds 20%, the storage stability of the curable composition decreases. Sometimes.

Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is used when particularly improving effects such as thixotropy of the compound, breaking strength of the cured product, elongation at break, adhesion and weather resistance adhesion are expected. Is preferred.
On the other hand, heavy calcium carbonate may be added for the purpose of lowering the viscosity of the compound, increasing the amount, reducing costs, etc. When using this heavy calcium carbonate, the following may be added as necessary. Can be used.

Heavy calcium carbonate is obtained by mechanically crushing and processing natural chalk (chalk), marble, limestone, and the like. There are dry and wet methods for the pulverization method, but wet pulverized products are often not preferred because they often deteriorate the storage stability of the curable composition of the present invention. Heavy calcium carbonate becomes products having various average particle sizes by classification. There is no particular limitation, but when the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product is expected, the value of the specific surface area is 1.5 m ² / g or more and 50 m ² / g or less. , more preferably from ^2m 2 / g or more ^{50 m} 2 / g or less, more preferably 2.4 m ² / g or more ^{50m 2 / g, 3m 2 /} g or more ^{50 m} 2 / g or less is particularly preferred. When the specific surface area is less than 1.5 m ² / g, the improvement effect may not be sufficient. Of course, this is not the case when the viscosity is simply lowered or when the purpose is to increase the viscosity only.

In addition, the value of the specific surface area means a measurement value by an air permeation method (a method for obtaining a specific surface area from air permeability with respect to a powder packed bed) performed according to JIS K 5101 as a measurement method. As a measuring instrument, it is preferable to use a specific surface area meter SS-100 manufactured by Shimadzu Corporation.

These fillers may be used alone or in combination of two or more according to the purpose and necessity. Although it is not particularly limited, for example, when heavy calcium carbonate with a specific surface area value of 1.5 m ² / g or more and collagen calcium carbonate are combined, the increase in viscosity of the compound is moderately suppressed. The effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product can be greatly expected.

When the filler is used, the addition amount is preferably 5 to 1000 parts, preferably 10 to 500 parts with respect to 100 parts in total of the components (A) and (B). It is more preferable to use it, and it is particularly preferable to use it in the range of 20 to 300 parts. If the blending amount is less than 5 parts, the effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product may not be sufficient, and if it exceeds 1000 parts, the workability of the curable composition May decrease. A filler may be used independently and may be used together 2 or more types.

<Adhesive resin>
Since the curable composition of the present invention is preferably composed mainly of a (meth) acrylic polymer, it is not always necessary to add an adhesion-imparting resin. Can be used. Specific examples include phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin and the like.
The amount of the adhesion-imparting resin used is 0.1 to 0.1 parts in total for the total of 100 parts of the component (A) and the component (B) from the viewpoint of the balance between the mechanical properties, heat resistance, oil resistance and adhesion of the cured product. 100 parts are preferred.

<Anti-aging agent>
In the curable composition of the present invention, an anti-aging agent may be blended in order to adjust physical properties.
An acrylic polymer is originally a polymer excellent in heat resistance, weather resistance, and durability, and therefore, an anti-aging agent is not necessarily required, but a conventionally known antioxidant and light stabilizer may be appropriately used. it can. Further, the anti-aging agent can be used for polymerization control during polymerization, and physical properties can be controlled.

Various types of antioxidants are known, and are described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242) published by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.
Examples of the antioxidant include thioethers such as MARK PEP-36 and MARK AO-23 (all are manufactured by Asahi Denka Co., Ltd.); Irgafos 38, Irgafos 168, Irgafos P-EPQ (all are Ciba Specialty And phosphorous antioxidants such as Chemicals Co., Ltd .; hindered phenolic compounds, and the like. Of these, hindered phenol compounds as shown below are preferred.

Specific examples of the hindered phenol compound include the following. 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α methylbenzyl) phenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4, 4′-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis- [3- (3- t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1 , 3,5-triazine, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-) t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-to Limethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl) calcium, tris -(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2 -[2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyl Enyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5 -Chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3 5-Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6- Ntamechiru 4-piperidyl), 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like.

In terms of product names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Also manufactured by Ouchi Shinsei Chemical Co., Ltd.), MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO- 80, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all are manufactured by Asahi Denka Co., Ltd.), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024 , IRG NOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all of which are manufactured by Ciba Specialty Chemicals Co., Ltd.), Sumilizer GA-80 (and above, Any of them can be exemplified by Sumitomo Chemical Co., Ltd.), but is not limited thereto.

Furthermore, a monoacrylate phenolic antioxidant having both an acrylate group and a phenol group, a nitroxide compound, and the like can be given.
Examples of the monoacrylate phenol-based antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name Sumilyzer GM), 2 , 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (trade name Sumitizer GS) and the like.

Nitroxide compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radicals and 2,2,5,5-substituted-1-pyrrolidinyloxy radicals, cyclic hydroxyamines, etc. The nitroxy free radicals from are illustrated. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or 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, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like.
Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

Antioxidants may be used in combination with light stabilizers, and when used together, the effects are further exerted, and the heat resistance may be particularly improved. Tinuvin C353, Tinuvin B75 (all of which are manufactured by Nippon Ciba Geigy Co., Ltd.) and the like in which an antioxidant and a light stabilizer are mixed in advance may be used.

The monoacrylate phenol-based antioxidant can control the rate and curability of thermal radical curing and improve the elongation of the cured product. Since the physical properties of the cured product can be easily controlled, the same examples as described above are exemplified. The said monoacrylate phenolic antioxidant may be used independently and may be used in combination of 2 or more type.

Although the usage-amount of the said various antioxidants including a monoacrylate phenolic antioxidant is not specifically limited, For the purpose of giving a good effect on the mechanical property of the hardened | cured material obtained, (A) component and (B ) 0.01 parts or more is preferable and 0.05 parts or more is more preferable with respect to 100 parts in total. Moreover, 5.0 parts or less are preferable, 3.0 parts or less are more preferable, and 2.0 parts or less are more preferable.

<Plasticizer>
You may mix | blend a plasticizer with the curable composition of this invention.
As a plasticizer, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, etc. Non-aromatic dibasic acid esters; esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphate esters such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; alkyl diphenyl; partial water Examples thereof include hydrocarbon oils such as terphenyl. These can be used alone or in admixture of two or more, but are not necessarily required. In addition, these plasticizers can also be mix | blended at the time of polymer manufacture.
The amount of the plasticizer used is preferably 5 to 800 parts with respect to a total of 100 parts of the component (A) and the component (B) from the viewpoint of imparting elongation, workability, and preventing bleeding from the cured product.

<Adhesion improver>
Various adhesive property improvers may be added to the curable composition of the present invention in order to improve the adhesiveness to various supports (plastic film or the like).
Examples of the adhesion improver include alkyl alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-mercaptopro Le trimethoxysilane, .gamma.-mercaptopropyl alkoxysilanes having a functional group such as a methyl dimethoxy silane; silicone varnishes; polysiloxanes and the like.
From the viewpoint of the balance between mechanical properties (elongation and strength) and adhesiveness of the cured product, the amount of the adhesive improver used is 0.1 to 20 with respect to 100 parts in total of the (A) component and the (B) component. Part is preferred.

<Preparation of curable composition>
The curable composition of the present invention can be prepared as a one-pack type in which all blending components are blended and sealed in advance, and the A liquid from which only the initiator is removed and the initiator is mixed with a filler, a plasticizer, a solvent, and the like. It can also be prepared as a two-component type in which the B liquid is mixed immediately before molding.

<< cured product >>
<Curing method>
Curing of the curable composition of the present invention is performed by using thermal radical curing and thermal cleavage cationic curing in combination. Specifically, a cured product can be obtained by radical curing by thermal initiation of the vinyl copolymer (A) and cationic curing by thermal cleavage of the epoxy compound and / or oxetane compound (B). .

<Heating temperature>
As heating temperature conditions, it implements at the temperature which the heat hardening of the said (A) component and (B) component advances. The temperature is preferably a temperature at which the composition can maintain a molten state. That is, 50 degreeC or more is preferable, 50-200 degreeC is more preferable, and 60-180 degreeC is further more preferable.

<< Usage >>
The use of the curable composition of the present invention is not particularly limited, but electrical and electronic component materials such as solar cell backside sealing materials, electrical insulating materials such as electric wire and cable insulation coating materials, coating materials, foams, It can be used for various applications such as potting materials for electrical and electronic use, films, gaskets, casting materials, artificial marble, various molding materials, meshed glass and sealing materials for rust prevention and waterproofing of laminated glass end faces (cut parts). is there.

The molded product showing rubber elasticity obtained from the curable composition of the present invention can be widely used mainly in gaskets and packings.
For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. Engine parts can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts.

In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake cans, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, etc., O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker gaskets, speaker edges, turntable systems for acoustic equipment such as diaphragm valves and air pipes Door, belts, pulleys, and the like.

In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like.
In the sports field, it can be used for all-weather pavement materials and gymnasium floors as sports floors, shoe sole materials and midsole materials as sports shoes, and golf balls as ball for ball games.
In the field of anti-vibration rubber, it can be used for anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials and the like.

In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for draging hoses, oil skimmers, etc.
In addition, it can be used for sheet rubber, mats, foam boards and the like.

<Preferable curable composition>
The polymer of component (A) is an acrylate polymer, and the main chain is preferably produced by living radical polymerization, preferably atom transfer radical polymerization. From the viewpoint of improving the strength of the cured product, imparting elongation, improving workability, and the like, it is effective to add an acrylate monomer. The epoxy compound and / or oxetane compound of component (B) preferably has no aromatic ring from the viewpoint of curability. Moreover, (C) thermal radical polymerization initiator is contained as the thermal polymerization initiator of component (A), and (D) thermal cleavage type cationic polymerization initiator is contained as the thermal polymerization initiator of component (B). Is preferred. Furthermore, strength and elongation can be further improved by adding a compound having both an epoxy group and a (meth) acryloyl group in the molecule (E) as a binder for the component (A) and the component (B). .

By using the thermal radical curing / thermal cationic curing combined curable composition of the present invention, the curability is excellent in heat resistance, weather resistance, oil resistance, etc., and has low viscosity and excellent strength characteristics when cured. A composition can be provided.

Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples.
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, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.
In the following examples, “average number of terminal (meth) acryloyl groups” is “number of (meth) acryloyl groups introduced per molecule of polymer”, and the number average molecular weight determined by ¹ H-NMR analysis and GPC. Calculated.
In the following examples, “part” represents “part by weight”.

Production Example 1 (Synthesis of acryloyl group both terminal poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate))
Cuprous bromide as catalyst, pentamethyldiethylenetriamine as ligand, diethyl-2,5-dibromoadipate as initiator, n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate in 25 / mole Polymerization was performed at a ratio of 46/29 to obtain a terminal bromine group poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) having a number average molecular weight of 21,000 and a molecular weight distribution of 1.16.
400 g of this polymer was dissolved in N, N-dimethylacetamide (400 mL), 10.7 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 6 hours under a nitrogen atmosphere. A mixture of butyl / ethyl acrylate / 2-methoxyethyl acrylate) (hereinafter referred to as polymer [1]) was obtained. After N, N-dimethylacetamide in the mixed solution was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. Toluene in the filtrate was distilled off under reduced pressure to purify the polymer [1].
The number average molecular weight of the purified acryloyl group both-end polymer [1] is 21400, the molecular weight distribution is 1.17, and the average terminal acryloyl group number is 1.8 (that is, the introduction rate of acryloyl group at the terminal is 90%). there were.

Example 1
70 parts of the polymer [1] obtained in Production Example 1 is 0.7 parts of Nyper BW (75% by weight of benzoyl peroxide, manufactured by Nippon Oil & Fats Co., Ltd.), Celoxide 2021P (3,4-epoxycyclohexylmethyl) -3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Chemical Industries, Ltd. 30 parts, Adeka Opton CP-77 (2-butenyltetramethylenesulfonium hexafluoroantimonate, thermal cleavage type cationic polymerization initiator, 0.45 parts, manufactured by Asahi Denka Kogyo Co., Ltd., IRGANOX 1010 (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], antioxidant, manufactured by Ciba Specialty Chemicals) 1 part was added and mixed well to obtain a curable composition.
Next, the obtained curable composition was pressed at a compression pressure of 5 MPa at 150 ° C. for 15 minutes using a compression molding machine (manufactured by Shindo Metal Industry Co., Ltd.), and a sheet-like cured product having a thickness of about 2 mm. Got.

Example 2
Add 50 parts of Nyper BW, 50 parts of Celoxide 2021P, 0.75 part of Adeka Opton CP-77 and 1 part of IRGANOX1010 to 50 parts of the polymer [1] obtained in Production Example 1 and mix thoroughly. Thus, a curable composition was obtained.
Next, using the obtained curable composition, a sheet-like cured product having a thickness of about 2 mm was obtained in the same manner as in Example 1.

Example 3
For 70 parts of the polymer [1] obtained in Production Example 1, 0.7 part of Nyper BW, ERL4299 (bis (3,4-epoxycyclohexylmethyl) adipate, manufactured by Dow Chemical Japan Co., Ltd.) 30 parts, 0.45 parts of Adeka Opton CP-77 and 1 part of IRGANOX 1010 were added and mixed well to obtain a curable composition.
Next, using the obtained curable composition, a sheet-like cured product having a thickness of about 2 mm was obtained in the same manner as in Example 1.

Comparative Example 1
To 100 parts of the polymer [1] obtained in Production Example 1, 1.0 part of Niper BW and 1.0 part of IRGANOX 1010 were added and mixed well to obtain a curable composition.
Next, using the obtained curable composition, a sheet-like cured product having a thickness of about 2 mm was obtained in the same manner as in Example 1.

Comparative Example 2
100 g of polyoxypropylene glycol having an end of alkenylation and a molecular weight of about 10,000, 6.9 g of a chain siloxane containing an average of 5 hydrosilyl groups and an average of 5 α-methylstyrene groups in the molecule, A curable composition was obtained by mixing 0.64 ml of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex at room temperature.
Next, using the obtained curable composition, a sheet-like cured product having a thickness of about 2 mm was obtained in the same manner as in Example 1 except that the pressing time was 10 minutes.

The viscosity of the curable compositions obtained in the above Examples and Comparative Examples and the mechanical properties of the cured products were measured as follows. The results are shown in Table 1.
(1) Viscosity The viscosity of the curable composition obtained above was measured using an E-type viscometer (VISCONIC ED type, manufactured by Tokyo Keiki Co., Ltd.) at a temperature of 23 ° C. using a 3 ° cone.
(2) Mechanical properties A No. 3 dumbbell was prepared using the sheet-like cured product obtained above, and mechanical properties were measured using the dumbbells according to the method of JIS K 6301. In Table 1, M30 represents the modulus at 30% elongation, Tb represents the strength at break, and Eb represents the elongation at break.

From the results in Table 1, the compositions of Examples 1 to 3 had low viscosity at 23 ° C. and good workability, but the composition of Comparative Example 1 had a high viscosity of 249 Pa · s at 23 ° C. Workability such as mixing and pouring was poor. Moreover, although the hardened | cured material of Examples 1-3 had high intensity | strength, the intensity | strength of the hardened | cured material of Comparative Examples 1-2 was low.

By using the thermal radical curing / thermal cationic curing combined curable composition of the present invention, the curability is excellent in heat resistance, weather resistance, oil resistance, etc., and has low viscosity and excellent strength characteristics when cured. A composition can be provided.

Claims (20)

(A) below Ri component and (B) Na contain components as essential components, a thermal radical curing / thermal cationic curing combination curable composition used in the molding of the gasket or packing,
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl monomer that has two or more groups represented by general formula (1) and has at least one group represented by the general formula (1) at the molecular end, and constitutes the main chain. Vinyl polymers that are acrylic monomers,
(B) an epoxy compound and / or an oxetane compound,
In addition to the component (A) and the component (B), (C) a thermal radical polymerization initiator and (D) a heat-cleavable cationic polymerization initiator ,
Wherein (C) thermal radical polymerization initiator, azo initiators, peroxide initiators or persulfate initiator curable compositions der characterized Rukoto. The curable composition according to claim 1, wherein the vinyl monomer constituting the main chain of the component (A) is an acrylate ester monomer. The curable composition according to claim 1 or 2, wherein the vinyl monomer constituting the main chain of the component (A) contains at least two selected from butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. R ^<a> in General formula (1) of (A) component is a hydrogen atom or a C1-C20 hydrocarbon group, The curable composition in any one of Claims 1-3. The curable composition according to claim 4, wherein R ^a in the general formula (1) of the component (A) is a hydrogen atom or a methyl group. (A) component is
To vinyl polymer having a halogen group at the molecular end,
General formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The curable composition in any one of Claims 1-5 manufactured by making the compound shown by react. A vinyl polymer having a halogen group at the molecular end is represented by the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to an ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
The curable composition of Claim 6 which has group shown by these. (A) component is
To vinyl polymer having a hydroxyl group at the molecular end,
General formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The curable composition in any one of Claims 1-5 manufactured by making the compound shown by react. (A) component is
(1) A diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at the molecular end,
(2) Residual isocyanate group and general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The curable composition in any one of Claims 1-5 manufactured by making it react with the compound shown by these. The curable composition according to any one of claims 1 to 9, wherein the main chain of the component (A) is produced by living radical polymerization of a vinyl monomer. The curable composition according to claim 10, wherein the living radical polymerization is atom transfer radical polymerization. The curable composition according to claim 11, wherein the transition metal complex which is a catalyst for atom transfer radical polymerization is selected from complexes of copper, nickel, ruthenium or iron. The curable composition according to claim 12, wherein the transition metal complex is a copper complex. The curable composition according to any one of claims 1 to 9, wherein the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent. The number average molecular weight of (A) component is 3000 or more and 100000 or less, The curable composition in any one of Claims 1-14. The curable composition according to any one of claims 1 to 15, wherein the vinyl polymer of the component (A) has a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is less than 1.8. Composition. The curable composition according to any one of claims 1 to 16 , wherein the epoxy compound or oxetane compound as component (B) does not have an aromatic ring. The curable composition according to any one of claims 1 to 17 , wherein the epoxy compound or oxetane compound as component (B) has an alicyclic structure. A gasket obtained by curing the curable composition according to claim 1. A packing obtained by curing the curable composition according to claim 1.