JP2006274099A - Curable composition for prepreg and prepreg obtained by curing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a curable composition for providing a prepreg having excellent heat resistance, oil resistance, weather resistance, chemical resistance and water resistance. <P>SOLUTION: The curable composition for a prepreg comprises (A) a vinyl-based polymer that has two or more groups represented by general formula (1) -OC(O)C(R<SP>a</SP>)=CH<SB>2</SB>(R<SP>a</SP>is a hydrogen atom or a 1-20C organic group) per molecule and one or more groups represented by the general formula (1) at a molecular terminal in the groups, (B) an initiator and (C) a reinforcing fiber as essential components. The prepreg is obtained by curing the same. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a prepreg cured composition and a prepreg. More specifically, the present invention relates to a prepreg cured composition and a prepreg containing, as essential components, a vinyl polymer having a (meth) acryloyl group at a molecular end, an initiator, and a reinforcing fiber.

  As prepreg resin, high pipe bending strength and high pipe torsion are used for sports and leisure such as epoxy resin, golf shaft, fishing rod, boat, etc. mainly for general purpose applications requiring relatively mild heat resistance, moisture resistance and chemical resistance. For FPR applications that require strength and low rigidity, epoxy resin, polyester resin, phenol resin, and bismaleimide resin and polyimide resin are used for applications that require high heat resistance such as automobiles, aircraft, and space applications. Yes.

  Although there is a report (Patent Document 1) regarding a resin composition for prepregs, a prepreg and a composite material containing an epoxy resin as a main component, relatively high temperature and long-time curing conditions are necessary, and it is not immediate curing. On the other hand, there is a report (Patent Document 2) in which the heat resistance, water resistance, and impact resistance of the epoxy resin are improved, but the Tg of the prepreg obtained by curing is increased to 200 ° C. or more and is inferior in flexibility. It was.

Furthermore, there is a report (Patent Document 3) in which solid rubber or a thermoplastic polymer is added to an epoxy resin to improve adhesion to the honeycomb (Patent Document 3), but it has not yet been possible to improve flexibility and give rubber elasticity.
JP-A-6-298908 JP-A-6-145473 JP 2004-346092 A

An object of this invention is to provide the curable composition which can provide the prepreg excellent in heat resistance, oil resistance, a weather resistance, chemical resistance, and water resistance, and the prepreg formed by hardening it.

The present invention relates to the following curable compositions for prepreg and prepregs obtained by curing the same.
(1) The following three components:
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, Ra 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 having one or more groups represented by the general formula (1) at the molecular terminals,
(B) an initiator, and
(C) A curable composition for a prepreg containing a reinforcing fiber as an essential component.
(2) The curable composition for prepregs according to (1), wherein the vinyl polymer of component (A) is a (meth) acrylic polymer.
(3) The component (A) is
To the vinyl polymer having a halogen group at the 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, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The curable composition for prepregs according to any one of (1) to (2), which is produced by reacting the compound represented by formula (1).
(4) A vinyl polymer having a halogen group at the 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 a vinyl-based monomer, X represents a chlorine atom, a bromine atom or an iodine atom) Curable composition.
(5) The component (A) is
To the vinyl polymer having a hydroxyl group at the 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, X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group) (1) to The curable composition for prepregs according to any one of (2).
(6) The component (A) is
(1) A diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at a terminal,
(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 for prepregs according to any one of (1) to (2).
(7) The curable composition for prepregs according to any one of (1) to (6), wherein the main chain of the component (A) is produced by living radical polymerization of a vinyl monomer.
(8) The curable composition for prepregs according to (7), wherein the living radical polymerization is atom transfer radical polymerization.
(9) The curable composition for prepreg according to (8), wherein the atom transfer radical polymerization is an organic halide or a sulfonyl halide compound as an initiator, and a transition metal complex selected from copper, nickel, ruthenium or iron complexes is a catalyst. object.
(10) The curable composition for prepregs according to (9), wherein the transition metal complex is a copper complex.
(11) The curable composition for prepreg according to any one of (1) to (6), wherein the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent.
(12) The curable composition for prepregs according to any one of (1) to (11), wherein the component (A) has a number average molecular weight of 3000 or more.
(13) Any of (1) to (12), 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. The curable composition for prepregs according to claim 1.
(14) The curable composition for prepregs according to any one of (1) to (13), which contains a monomer and / or an oligomer having a radical polymerizable group as the component (D).
(15) The curable composition for prepregs according to any one of (1) to (13), which contains a monomer and / or oligomer having an anion polymerizable group as component (D).
(16) The curable composition for prepregs according to any one of (14) to (15), which contains a monomer and / or an oligomer having a (meth) acryloyl group as the component (D).
(17) The curable composition for prepregs according to (16), wherein the component (D) has a (meth) acryloyl group and further contains a monomer and / or an oligomer having a number average molecular weight of 5000 or less.
(18) The curable composition for prepregs according to any one of (1) to (17), wherein the initiator of the component (B) is a radical initiator.
(19) The curable composition for prepregs according to any one of (1) to (17), wherein the initiator of the component (B) is an anionic initiator.
(20) The curable composition for prepregs according to any one of (1) to (17), wherein the initiator of the component (B) is a redox initiator.
(21) The curable prepreg according to any one of (1) to (20), wherein the component (C) is at least one selected from the group consisting of glass fiber, carbon fiber, and aramid fiber. Sex composition.
(22) A prepreg obtained by curing the curable composition for prepreg according to any one of (1) to (21).
(23) A prepreg obtained by irradiating the curable composition for prepreg according to any one of (18), (19), and (21) with active energy rays.
(24) A prepreg obtained by heat curing the prepreg curable composition according to any one of (18), (19), and (21).
(25) A prepreg obtained by curing the prepreg curable composition of (20) or (21) in a two-component system at room temperature.

  According to the prepreg curable composition of the present invention, a prepreg excellent in heat resistance, oil resistance, weather resistance, chemical resistance and water resistance can be obtained.

The curable composition for prepreg and the prepreg obtained by curing it are described below.
The curable composition for prepregs of the present invention is characterized by containing the following components (A), (B) and (C) as essential components.
The component (A) is represented by the general formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, Ra 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 having one or more groups represented by the general formula (1) at the molecular terminals,
(B) component: an initiator, and
(C) Component: Reinforcing fiber.
<(A) component>
The component (A) is represented by the general formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, Ra represents ^a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Is a vinyl polymer having 2 or more groups per molecule, and having 1 or more groups represented by the general formula (1) at the molecular terminals.

The number of groups ((meth) acryloyl group) represented by the 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. Sometimes. 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 at the molecular end.

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 (preferably obtaining rubber elasticity by setting it to 500 to 100,000), a form close to the other molecular end is preferable, and a form close to the other molecular end is preferable. .

^Ra 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 aryl groups having 6 to 20 carbon atoms such as 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 aralkyl group having 7 to 20 carbon atoms such as phenyl group and naphthyl group include benzyl group and phenylethyl group.

Specific 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 are mentioned, and preferably —H, —CH ₃ .

  (A) There is no limitation in particular in the 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 acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxy) propyltrimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2 -Perfluoroethylethyl, 2- (perfluoroethyl) 2- (perfluoroethyl) (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, di (meth) acrylate Perfluoromethyl methyl, 2-meth (meth) acrylic acid 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 salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and di Kill esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; containing nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; 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 And conjugated dienes such as isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. 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. Further, from the viewpoint of oil resistance in the prepreg, the vinyl monomer constituting the main chain particularly preferably contains 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.

  The molecular weight distribution of component (A) (ratio of weight average molecular weight (Mw) and 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, a polystyrene gel column is usually used with chloroform or tetrahydrofuran as a mobile phase, 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. When the molecular weight is less than 500, the original characteristics of the vinyl polymer tend to be hardly expressed, and when 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, and 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 an azo compound or peroxide is used as a polymerization initiator, and a monomer having a specific functional group and a vinyl monomer are simply copolymerized. Can be classified into “radical polymerization methods” and “controlled radical polymerization methods” in which specific functional groups can be introduced at controlled positions such as terminals.

  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, and conversely, in the case of using a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced becomes large. 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, It can be classified as “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing the terminal 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, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, 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.

  In the narrow sense, living polymerization refers to 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. “Atom transfer radical polymerization” using radical scavengers such as nitroxide compounds as shown in Macromolecules, 1994, 27, 7228, organic halides as initiators and transition metal complexes as catalysts. (Atom Transfer Radical Polymerization: ATRP).

  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 characteristics 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. Therefore, 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, And the method described on page 1721.

  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 standpoint of ease of control. The transfer radical 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 of 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 thereof include 1,1,3,3-tetramethyl-2-isoindolinyloxy radical and N, N-di-t-butylamineoxy radical.

  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 there is no limitation in the usage ratio of both, 0.1-10 mol of radical initiators are suitable with respect to 1 mol of radical capping agents.

  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, Examples thereof include peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctoate 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.

アルコキシアミン化合物を開始剤として用いる場合、それが前記のような水酸基などの官能基を有するものを用いると末端に官能基を有する重合体が得られる。これを本発明に利用すると、末端に官能基を有する重合体が得られる。

When an alkoxyamine compound is used as an initiator, a polymer having a functional group at the terminal can be obtained by using an alkoxyamine compound having a functional group such as a hydroxyl group as described above. When this is used in the present invention, a polymer having a functional group at the terminal can be 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 a halogen at the α-position or a compound having a halogen at the benzyl-position), or a halogen Sulfonyl compounds and the like are used as initiators.

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. For example, the general formula (6):
R ⁶ R ⁷ C (X) —R ⁸ —R ⁹ —C (R ⁵ ) ═CH ₂ (6)
(Wherein 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 the like. Connected to each other at the ends, R ⁸ is —C (O) O— (ester group), —C (O) — (keto group), or o-, m-, p-phenylene group, R ⁹ is directly A divalent organic group having 1 to 20 carbon atoms which may contain a bond or one or more ether bonds, X is a chlorine atom, a bromine atom or an iodine atom)
What is shown by this 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. Examples thereof include an alkylene group.

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

（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、ｎは０〜２０の整数）
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、
Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、
（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、
ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂

(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

（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂
（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_mＣＨ＝ＣＨ₂
（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂
（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂
（以上の式中、Ｘは塩素原子、臭素原子またはヨウ素原子、ｎは１〜２０の整数、ｍは０〜２０の整数）
前記アルケニル基を有する有機ハロゲン化物としては、さらに一般式（７）：
Ｈ₂Ｃ＝Ｃ（Ｒ⁵）−Ｒ⁹−Ｃ（Ｒ⁶）（Ｘ）−Ｒ¹⁰−Ｒ⁷ （７）
（式中、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁹、Ｘは前記に同じ、Ｒ¹⁰は、直接結合、−Ｃ（Ｏ）Ｏ−（エステル基）、−Ｃ（Ｏ）−（ケト基）またはｏ−，ｍ−，ｐ−フェニレン基を表わす）
で示される化合物があげられる。

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1 to 20, and m is an integer of 0 to 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 to 20, and m is an integer of 0 to 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 formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1 to 20, and m is an integer of 0 to 20)
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 and 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 mention | raise | lifted.

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), but in the case of a direct bond, a halogen atom is bonded. A vinyl group is bonded to carbon, which is an allyl halide. 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 or a phenylene group 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)
(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , and X are the same as described above, and R ¹¹ and R ¹² are all alkyl groups, aryl groups, aralkyl groups, or C 1-20. (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). Represents an organosiloxy group, and 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 represents 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 Satisfied to be)
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 or iodine atom, n is an integer of 0 to 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
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1 to 20, and m is an integer of 0 to 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 and Y are the same as above, m is an integer of 0 to 19)
What is shown by this 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 sulfonyl halide 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.

（式中、Ｘは塩素原子、臭素原子またはヨウ素原子、Ｒは水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
一般式（１）で表わされる基を１分子あたり２個以上、分子末端に有するビニル系重合体を得るためには、２個以上の開始点を有する有機ハロゲン化物またはハロゲン化スルホニル化合物を開始剤として用いるのが好ましい。具体的に例示するならば、

(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,

などがあげられる。

Etc.

  There is no restriction | limiting in particular in the vinyl-type monomer used in the said 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 group 7 element, group 8, group 9, group 10, or group 11 element as a central metal, such as copper, It is a complex of nickel, ruthenium and iron. Further preferred are 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 and the like. Can be given.

  In the case of using a copper compound, 2,2′-bipyridyl, its derivative, 1,10-phenanthroline, its derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. to increase the catalytic activity A ligand such as a 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.

Furthermore, 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>
There are no particular limitations on the method for producing the component (A). For example, a vinyl polymer having a reactive functional group is produced 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) Vinyl-based polymer having a halogen group at the terminal, and 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, 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 the 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, 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-based 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, 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).

  Although there is no limitation in particular in the vinyl polymer which has a halogen group at the terminal, What has a terminal group shown in General formula (3) is preferable.

  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 ^Ra in the general formula (2) are the same as those described above, and specific examples thereof are also the same as those described above.

M ⁺ in the general formula (2) is a counter cation of an oxyanion, and examples thereof include alkali metal ions and quaternary ammonium ions.

  Examples of the alkali metal ion include lithium ion, sodium ion, and potassium ion. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, and tetrabutyl. Examples thereof include ammonium ion and dimethylpiperidinium ion. 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 ^Ra in General Formula (4) are the same as those described above, and specific examples thereof are also 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. Although it is produced by a method of polymerizing a vinyl monomer, the former is preferred.

  The method for producing the vinyl polymer having a hydroxyl group at the terminal is not particularly limited, but examples thereof include the following methods.

(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)
Wherein 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.

  There is no restriction on the timing for 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, the second monomer has a low polymerizable alkenyl group and hydroxyl group as the second monomer after 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 such a 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 above, and R ¹⁶ represents a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds.)
And the like.

  The compound represented by the general formula (11) is not particularly limited, but alkenyl alcohols such as 10-undecenol, 5-hexenol and allyl alcohol are preferable because they are easily available.

  (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 hydrolyzing or reacting a halogen atom 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)
(Wherein, R ¹⁶ and M ⁺ are as defined above, R ^17, R ¹⁸ together carbanion C ^- with an electron withdrawing group or one of the electron-withdrawing group stabilizing, the other is a hydrogen atom, C1-10 Represents an alkyl group or a phenyl group of
A method of replacing halogen by reacting a stabilized carbanion having a hydroxyl group represented by

As the electron-withdrawing group, -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, —CO ₂ R, —C (O) R, —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 alone 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
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. 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 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, 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 ^Ra in General Formula (5) are the same as those described above, and specific examples thereof are also 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 alkylene groups 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 mention | raise | lifted.

  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. Examples thereof include xylylene diisocyanate and isophorone diisocyanate. These may be used alone or in combination of two or more. Moreover, you may use block isocyanate. From the viewpoint of obtaining superior 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, relative to the terminal hydroxyl group of the vinyl polymer.

  The reaction solvent is not particularly limited, but an aprotic solvent is preferred.

  Although there is no limitation in reaction temperature, Preferably it is 0-250 degreeC, More preferably, it is 20-200 degreeC.

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.
<(B) component>
(B) Although there is no limitation in particular as an initiator of a component, there exist a radical initiator, an anionic initiator, and a redox initiator.

  The radical initiator includes a thermal radical initiator that initiates polymerization by heat and a photopolymerization initiator that initiates polymerization by light.

  Although there is no restriction | limiting in particular in a thermal-polymerization initiator, An azo initiator, a peroxide, and a persulfuric acid are contained.

    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) (from Wako Pure Chemical) For example).

  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, and ammonium persulfate.

  A preferred thermal radical initiator is selected from the group consisting of azo initiators and peroxide initiators. More preferred are 2,2'-azobis (methylisobutylate), t-butyl peroxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

  The thermal initiator used in the present invention is present in a catalytically effective amount, and such amount is typically, but not limited to, a polymer having an acrylic functional group at at least one end of the present invention. When the total amount of the combined monomer and other monomer and oligomer mixture is 100 parts by weight, it is about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight.

The thermal polymerization initiators may be used alone or in combination of two or more.
When a mixture of initiators is used, the total amount of initiator mixture is preferably within the above range.

  The method for curing the curable composition using the thermal polymerization initiator of the present invention is not particularly limited, but the temperature varies depending on the type of thermal initiator used, but is usually preferably in the range of 50 ° C to 250 ° C. More preferably, the temperature is in the range of 70 ° C to 200 ° C. The curing time varies depending on the polymerization initiator, monomer, solvent, reaction temperature, etc. used, but is usually in the range of 1 minute to 10 hours.

The photo radical initiator is not particularly limited. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3- Pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophene, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4 '-Dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin Benzoin methyl ether, benzoin butyl ether, benzoin isobutyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1 -Hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, bisphenyl (2,5-dimethylbenzoyl) phosphine oxide, and the like.
These initiators may be used alone or in combination with other compounds. Specifically, combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combinations with iodonium salts such as diphenyliodonium chloride, and combinations with dyes and amines such as methylene blue, etc. can give.

  In addition, when using the said photoradical initiator, polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl catechol, can also be added as needed.

  Moreover, you may use a near-infrared light absorptive cationic dye as a near-infrared photoinitiator.

  Near-infrared light absorbing cationic dyes are excited by light energy in the region of 650 to 1500 nm, for example, near-infrared light disclosed in JP-A-3-111402, JP-A-5-194619, etc. It is preferable to use an absorbing cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer together.

  The addition amount of the photopolymerization initiator is not particularly limited because it only needs to slightly photofunctionalize the system, but is preferably 0.001 to 10 parts with respect to 100 parts of component (A).

  The anion initiator includes a thermal anion initiator that initiates polymerization with heat and a photoanion initiator that initiates polymerization with light.

  Examples of the thermal anion initiator include amines such as trimethylamine and triethylamine.

  The addition amount is about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight when the total amount of the monomer and oligomer mixture is 100 parts by weight.

The thermal polymerization initiators may be used alone or in combination of two or more.
When a mixture of initiators is used, the total amount of initiator mixture is preferably within the above range.

  The method for curing the curable composition using the thermal polymerization initiator of the present invention is not particularly limited, but the temperature varies depending on the type of thermal initiator used, but is usually preferably in the range of 50 ° C to 250 ° C. More preferably, the temperature is in the range of 70 ° C to 200 ° C. The curing time varies depending on the polymerization initiator, monomer, solvent, reaction temperature, etc. used, but is usually in the range of 1 minute to 10 hours.

  Examples of the photoanion initiator include 1,10-diaminodecane, 4,4′-trimethylenepiperazine, carbamates and derivatives thereof, cobalt-amine complexes, aminooxyiminos, and ammonium borates.

  These initiators may be used alone or in combination with other compounds. Specifically, combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combinations with iodonium salts such as diphenyliodonium chloride, and combinations with dyes and amines such as methylene blue, etc. can give.

  In addition, when using the said photoradical initiator, polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl catechol, can also be added as needed.

Curing conditions, addition amount, and the like are the same as those of the photo radical initiator.
Furthermore, examples of the initiator of the component (B) include redox initiators. Redox (redox) initiators can be used in a wide temperature range. In particular, the following initiator species can be advantageously used at room temperature.

The redox initiator is not limited, but a combination of the persulfate initiator and a reducing agent (sodium metabisulfite and sodium bisulfite); an organic peroxide and a tertiary amine. Combinations such as benzoyl peroxide and dimethylaniline; organic hydroperoxides and tertiary amines such as cumene hydroperoxide / butyraldehyde and aniline condensates, cumene hydroperoxide / dimethylaniline; metal complexes and tertiary amines Combinations such as copper naphthate / butyraldehyde and aniline condensates, other metal soap / butyraldehyde and aniline condensates combinations; and systems based on organic hydroperoxides and transition metals such as cumene hydroperoxide / cobalt naphthate Cumenehide Peroxide / copper naftate, tertiary butyl hydroperoxide / cobalt naphthenate Tate, tertiary butyl hydroperoxide / copper based naftate, further combination with other hydroperoxide / other metal soaps preferably,
From the viewpoint of curability and storage stability, a system based on an organic peroxide and a tertiary amine, or a combination of an organic hydroperoxide and a transition metal is more preferable.

When a redox initiator is used as the component (B), the redox initiator is present in a catalytically effective amount, and its addition amount is not particularly limited, but can 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 by weight, it is preferably about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight.
The redox initiators may be used alone or in combination of two or more.
When a mixture of initiators is used, the total amount of the initiator mixture is preferably within the above range.
<(C) component>
In order to increase the strength of the prepreg, reinforcing fiber is used as the component (C). (C) is not particularly limited, but carbon fiber, graphite fiber, glass fiber, aramid fiber, boron fiber, polyester fiber, polyethylene fiber, polybenzimidazole fiber, silicon carbide fiber, silicon carbide fiber, alumina fiber, silica alumina. Fiber, titania fiber and the like.

  The shape of the reinforcing fiber includes a tape shape, a sheet shape, a mat shape, and a woven fabric, and any shape may be used.

Among these, carbon fiber, glass fiber, and aramid fiber are preferable from the balance of price, heat resistance, and strength.
<(D) component>
For the purpose of improving the surface property of the prepreg obtained by curing the curable composition for prepreg of the present invention, imparting toughness, lowering the viscosity for improving the impregnation property of the reinforcing fiber (C), etc. As the component (D), a polymerizable monomer and / or oligomer can be used in combination.

  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 reactivity.

  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. And vinyl group. Especially, what has the (meth) acrylic-type group similar to the polymer used for this invention is preferable.

  Examples of the anionic polymerizable group include (meth) acryloyl groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, and vinyl ketone groups. Especially, what has the (meth) acryloyl type group similar to the polymer used for this invention is preferable.

  Specific examples of the monomer include (meth) acrylate monomer, cyclic acrylate, N-vinyl pyrrolidone, styrene monomer, acrylonitrile, N-vinyl pyrrolidone, acrylamide monomer, conjugated diene monomer, vinyl ketone monomer, polyfunctional monomer Etc.

  (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- (methacryloyloxy) propyltrimethoxysilane, (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.

スチレン系モノマーとしては、スチレン、α−メチルスチレンなどが、アクリルアミド系モノマーとしては、アクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミドなどが、共役ジエン系モノマーとしては、ブタジエン、イソプレンなどが、ビニルケトン系モノマーとしては、メチルビニルケトンなどがあげられる。

Styrene monomers include styrene and α-methylstyrene, acrylamide monomers include acrylamide and N, N-dimethylacrylamide, conjugated diene monomers include butadiene and isoprene, and vinyl ketone monomers. And methyl vinyl ketone.

  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 and the like.

  As the oligomer, epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolak type epoxy acrylate resin, cresol novolak 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 dii A urethane resin obtained from cyanate, xylylene diisocyanate, etc.) with 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 (meth) acrylic group is introduced into the polyol via an ester bond; polyester acrylate resin, (meth) acrylic ester polymer with (meth) acrylic group Introduced resin; poly (meth) acrylate resin (poly (meth) acrylate resin having a polymerizable reactive group) and the like.

  Of these, 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. Further, 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.

  The amount of the polymerizable monomer and / or oligomer used is 1 to 200 parts with respect to 100 parts by weight of the component (A) (hereinafter also simply referred to as “parts”) because of the improvement in surface curability and the provision of toughness. Is preferable, and 5 to 100 parts is more preferable.

Furthermore, the curable composition for prepregs of the components (A) to (C) or the components (A) to (D) can be blended with an epoxy resin, and the flexibility and oil resistance of a conventional prepreg based on an epoxy resin. , Weather resistance and the like can be improved.
<Reinforcing silica>
In the prepreg composition of the present invention, addition of reinforcing silica is useful from the viewpoint of further 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 below-mentioned.

  Further, surface-treated silica such as organosilane, organosilazane, diorganocyclopolysiloxane and the like is more preferable because it is easy to exhibit fluidity suitable for molding.

  More specific examples of the reinforcing silica system are not particularly limited. However, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Industry Co., Ltd., which is one of precipitated silicas. Nipsil and the like.

  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, It is preferable to use 0.1-100 parts with respect to 100 parts of said (A) component, Preferably it is 0.5-80 parts, Especially it is preferable to use 1-50 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 composition may be deteriorated.
<Filler>
In the curable composition for prepregs 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 acid anhydride, Hydrous silicic acid), reinforcing filler such as carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide , Filler, aluminum powder, flint powder, zinc oxide, activated zinc white, zinc powder, zinc carbonate and shirasu balloon, etc .; asbestos, glass fiber and glass filament, carbon fiber, kevlar fiber, polyethylene fiber, etc. Examples of such fibrous fillers. 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.

  Examples of the surface treatment agent include 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. 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, and oleic acid. And sodium salts and potassium salts of these fatty acids and alkyl esters of these fatty acids. Specific examples of surfactants include sulfuric acid ester type anionic surfactants such as sodium salts and potassium salts such as polyoxyethylene alkyl ether sulfates and long chain alcohol sulfates, 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 treated in the range of 0.1 to 20%, more preferably in the range of 1 to 5% with respect to calcium carbonate. When the treatment amount is less than 0.1%, the workability, adhesiveness and weatherability may not be improved sufficiently, and when it exceeds 20%, the storage stability of the composition may be lowered. is there.

  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, use the following as necessary. be able to.

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 pulverization methods, but wet pulverized products are often not preferred because they often deteriorate the storage stability of the composition of the present invention. Heavy calcium carbonate becomes a product having various average particle diameters 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 specific surface area value 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 preferable. 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 there is no particular limitation, for example, if heavy calcium carbonate and colloidal calcium carbonate having a specific surface area of 1.5 m ² / g or more are combined as necessary, the increase in viscosity of the compound is moderately suppressed, and a cured product is obtained. The effect of improving the breaking strength, breaking elongation, adhesiveness and weathering adhesion can be greatly expected.

When the filler is used, the addition amount is preferably 5 to 1000 parts, more preferably 20 to 500 parts, with respect to 100 parts of component (A), It is particularly preferable to use in the range of 40 to 300 parts. If the blending amount is less than 5 parts, the effect of improving the breaking strength, breaking elongation, adhesiveness and weather resistance of the cured product may not be sufficient, and if it exceeds 1000 parts, the workability of the composition is lowered. Sometimes. A filler may be used independently and may be used together 2 or more types.
<Adhesion imparting resin>
Since the curable composition for prepregs of the present invention is preferably composed mainly of a (meth) acrylic polymer, it is not always necessary to add an adhesion-imparting resin. Things can be used. Specific examples include rosin resin, terpene resin, coumarone resin, petroleum resin, and the like. Examples of the rosin resin include rosin; rosin ester resins such as rosin ester and hydrogenated rosin ester.

  Examples of the terpene resin include terpene phenol resin, aromatic modified terpene resin, hydrogenated terpene resin, and the like.

  Examples of petroleum resins include aliphatic, alicyclic and aromatic resins made from petroleum. Specifically, C5 petroleum resin, C9 petroleum resin, copolymer petroleum resin, alicyclic saturated hydrocarbon resin, phenol resin (phenol resin, modified phenol resin, cyclopentadiene-phenol resin), styrene resin, xylene Examples thereof include resins and indene resins.

The amount of the adhesion-imparting resin used is preferably 0.1 to 100 parts with respect to 100 parts of component (A) from the viewpoint of the balance between mechanical properties, heat resistance, oil resistance and adhesiveness of the prepreg.
<Anti-aging agent>
An anti-aging agent may be added to the prepreg curable composition of the present invention in order to adjust the physical properties.

  The 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 conventionally known antioxidants and light stabilizers can be appropriately used. . The anti-aging agent can also be used for polymerization control during polymerization, and can control physical properties. 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 mention | raise | lifted, it is not necessarily limited to these. For example, thioethers such as MARK PEP-36 and MARK AO-23 (all manufactured by Adeka Gas Chemical Co., Ltd.), Irgafos 38, Irgafos 168, Irgafos P-EPQ (all manufactured by Ciba Geigy Japan) And phosphorus-based antioxidants. Of these, hindered phenol compounds as shown below are preferred. The following can be illustrated as a specific example of a hindered phenol type compound. 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 (4methyl-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-4hydroxyphenyl) 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, pentaerythrityl-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-trime Til-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate 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-hydroxypheny L) 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-pen) Methyl 4-piperidyl), e.g., 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate and the like.

  In terms of trade 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 manufactured by Adeka Argus Chemical Co., Ltd.), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX- 10 4, IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all of these are manufactured by Ciba Geigy Japan), Sumitizer GA-80 (all of which are Sumitomo Chemical) But not limited to these. Furthermore, monoacrylate phenolic antioxidants having both acrylate groups and phenol groups, nitroxide compounds and the like can be mentioned. Examples of the monoacrylate phenol-based antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name Sumilizer GM), 2, Examples include 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (trade name: Sumilizer GS).

  Nitroxide compounds include, but are not limited to, cyclic hydroxyamines such as 2,2,6,6-substituted-1-piperidinyloxy radicals and 2,2,5,5-substituted-1-pyrrolidinyloxy radicals. 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 are particularly preferred because they can further exert their effects and in particular improve the heat resistance. Tinuvin C353, tinuvin B75 (all of which are manufactured by Nippon Ciba Geigy Co., Ltd.) or the like in which an antioxidant and a light stabilizer are mixed in advance may be used.

  When a prepreg is prepared by photo-radical curing using a vinyl polymer having a (meth) acryloyl group in the molecule, the polymerization proceeds quickly, so that the control is difficult. In some cases, the mechanical strength of the obtained prepreg is insufficient. As a method of controlling the polymerization, by making the functional group involved in the polymerization an acryloyl group, the polymerizability can be lowered as compared with the case of the methacryloyl group, but in this case, the polymerizability is often extremely lowered. Not practical. In general, a polymerization inhibitor may be used, but this is for the purpose of suppressing the polymerization itself and is not suitable for controlling the polymerization. On the other hand, in order to improve the heat resistance and weather resistance of the obtained prepreg, an anti-aging agent may be added, but this is not used for the purpose of improving the initial physical properties of the prepreg.

The monoacrylate phenol-based antioxidant not only serves as an antioxidant but also can control polymerization, and can improve the mechanical properties (elongation-strength balance) of the prepreg. Since the physical property control of a prepreg can be easily performed, the same thing as the above-mentioned is illustrated. The monoacrylate phenolic antioxidant may be used alone or in combination of two or more.
Although the usage-amount of the said various antioxidants including a monoacrylate phenolic antioxidant is not specifically limited, Aiming at giving the effect with a favorable mechanical physical property of the obtained prepreg with respect to 100 parts of (A) component Is preferably 0.01 or more, more preferably 0.05 part or more. Moreover, 5.0 parts or less and 3.0 parts or less are more preferable, and 2.0 parts or less are more preferable.
<Plasticizer>
A plasticizer component can be blended for the purpose of reducing the viscosity for improving the impregnation of the component (C) into the reinforcing fiber.

  As plasticizers, phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, etc .; non-dioctyl adipate, dioctyl sebacate, etc. Aromatic dibasic acid esters; Polyalkylene glycol esters such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Chlorinated paraffins; Alkyl diphenyl and partially hydrogenated Hydrocarbon oils such as terphenyl can be used alone or in admixture of two or more, but this is not always necessary. These plasticizers can also be blended at the time of polymer production.

The use amount of the plasticizer is preferably 5 to 800 parts with respect to 100 parts of the component (A) from the viewpoint of imparting elongation, impregnation into the component (C), and preventing bleeding from the prepreg.
<Solvent>
From the viewpoint of impregnation of component (C) into reinforcing fibers and drying before and after curing, an organic solvent may be added.

  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.

As the usage-amount of a solvent, 1-900 parts is preferable with respect to 100 parts of (A) component from a viewpoint of the finishing property of a foam, the impregnation property to a reinforced fiber, and drying property.
<Adhesion improver>
In addition, various adhesion improvers may be added to the prepreg composition of the present invention in order to improve the adhesion to various supports (metal, plastic, mortar, concrete, slate, etc.).

  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-mercaptop Pills trimethoxysilane, alkoxysilanes having a functional group such as γ- mercaptopropyl methyldimethoxysilane; silicone varnishes; polysiloxanes and the like.

The amount of the adhesion-imparting agent used is preferably 0.1 to 20 parts with respect to 100 parts of component (A) from the viewpoint of the balance between mechanical properties (elongation and strength) and adhesiveness of the prepreg.
<Preparation of curable composition for prepreg>
The prepreg curable composition of the present invention can be prepared as a one-pack type in which all the formulations are pre-blended and sealed, and the liquid A from which only the initiator is removed and the initiator is mixed with a filler, a plasticizer, a solvent and the like. A two-component type in which the prepared B liquid is mixed immediately before the prepreg is cured can also be adjusted.
<Prepreg>
The prepreg is obtained by curing the prepreg curable composition by normal temperature, heating, and light. Moreover, the hardening method may be individual and can use 2 or more types together. The obtained prepreg exhibits lighter weight, higher strength, and higher rigidity than metal materials, and can also improve defects peculiar to metals such as embrittlement at low temperatures.

The method for curing the prepreg curable composition is not particularly limited.
(B) When using a photoinitiator as a component, it can be hardened by irradiating light or an electron beam with an active energy ray source.

There is no particular limitation on the source of active energy rays, but depending on the nature of the photopolymerization initiator, for example, high-pressure mercury lamp, low-pressure mercury lamp, electron beam irradiation device, halogen lamp, light-emitting diode, semiconductor laser, etc. Irradiation.
When a photoinitiator is used as the component (B), the curing temperature is preferably 0 ° C to 150 ° C, more preferably 5 ° C to 120 ° C.
When a thermal polymerization initiator is used as the component (B), the curing temperature varies depending on the type of the thermal polymerization initiator used, the component (A), and other compounds to be added, but is usually preferably 50 to 250 ° C. 70 ° C to 200 ° C is more preferable.
When a redox initiator is used as the component (B), the curing temperature is preferably −50 ° C. to 250 ° C., more preferably 0 ° C. to 180 ° C.

  Moreover, although hardening time changes with the said initiator used, a monomer, a solvent, reaction temperature, etc., 1 minute-10 hours are preferable normally.

For the production of the prepreg curable composition and the prepreg of the present invention, production equipment using an epoxy resin or the like can be usually used. Although there is no limitation in particular as manufacturing equipment, it can manufacture using a resin mixer, a film manufacturing machine, a hardening apparatus (a heating furnace, UV irradiation apparatus, etc.), etc.
<Application>
Specific uses of prepreg include, for example, leisure use such as golf shaft fishing rods and boats, FPR use, automobiles, aircraft, space use, etc., interlayer insulation for rotating machines, transformers and controllers, industrial products and electronic parts bonding Etc.

  By using the curable composition for prepreg of the present invention, a prepreg excellent in heat resistance, oil resistance, weather resistance, chemical resistance and water resistance 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, the number average molecular weight and the molecular weight distribution (ratio of the weight average molecular weight to the number average molecular weight) were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). A GPC column filled 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, the average number of terminal (meth) acryloyl groups is the number of (meth) acryloyl groups introduced per molecule of polymer, and is calculated based on the number average molecular weight determined by ¹ H NMR analysis and GPC. did.
Production Example 1 (Synthesis of poly (acryloyl group) -terminated 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 16,500 and a molecular weight distribution of 1.13.

  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. The 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-terminated polymer [1] is 16900, the molecular weight distribution is 1.14, 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.
Production Example 2 (Synthesis of acryloyl group single terminal poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate))
Cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand, ethyl 2-bromobutyrate as an initiator, and n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate in moles of 25/46/29 Polymerization was carried out at a ratio of 1 to 3, thereby obtaining a one-terminal bromine group poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) having a number average molecular weight of 3700 and a molecular weight distribution of 1.14.

  1050 g of this polymer was dissolved in N, N-dimethylacetamide (1050 g), 56.2 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 4 hours under a nitrogen atmosphere. A mixture of butyl / ethyl acrylate / 2-methoxyethyl acrylate) (hereinafter referred to as polymer [2]) was obtained. N, N-dimethylacetamide in the mixture was distilled off under reduced pressure, toluene was added to the residue, and insolubles were removed by filtration. The toluene in the filtrate was distilled off under reduced pressure to purify the polymer [2].

  The number average molecular weight of the purified acryloyl group single terminal polymer [2] is 3800, the molecular weight distribution is 1.15, and the average terminal acryloyl group number is 1.0 (that is, the introduction rate of acryloyl group at the terminal is almost 100%) Met.

Example 1
100 parts of the polymer [1] obtained in Production Example 1, 1 part of Irgacure 184 (1-hydroxycyclohexyl-phenyl ketone) (manufactured by Ciba Specialty Chemicals), Irgacure 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine Oxide) (made by Ciba Specialty Chemicals) 0.5 part, Irganox 1010 (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]) (made by Ciba Specialty Chemicals) The mixture was thoroughly mixed and impregnated into 30 parts of glass fiber to obtain a curable composition for prepreg.

  Next, the obtained curable composition was irradiated with light for 30 seconds with a metal halide lamp (80 W / cm, irradiation distance 15 cm, belt speed 1.0 m / min) to obtain a sheet-like cured product having a thickness of about 2 mm. .

  The obtained cured product was evaluated for tensile properties, heat resistance, oil resistance, chemical resistance, water resistance and weather resistance by the following methods. The results are shown in Table 1.

[Tensile properties: breaking strength and breaking elongation]
A No. 2 dumbbell was produced from the obtained cured product, and using this, in accordance with JIS K 7113, Shimadzu autograph (AG-2000A) test speed 200 mm / min, 23 ° C. × 55% R.D. H. Tensile properties were measured under the following conditions.

  In Table 1, TB indicates the breaking strength and EB indicates the breaking elongation.

[Heat resistance, oil resistance, weather resistance, chemical resistance, water resistance]
The obtained cured product was cut into a size of 30 mm × 30 mm × 2 mm thickness, and various properties were evaluated as follows.

  (1) Heat resistance: After holding at 150 ° C. for 1000 hours, the appearance of the cured product was visually confirmed.

  (2) Oil resistance: 150 ° C. x 70 hours After immersion in engine oil (IRM903; manufactured by Nippon San Oil), the appearance of the cured product was visually confirmed.

  (3) Chemical resistance: After dipping in a 10% aqueous sulfuric acid solution at 23 ° C. for 30 days, the appearance of the cured product was confirmed.

  (4) Water resistance; after being immersed in water at 23 ° C. for 7 days, the appearance of the cured product was visually confirmed.

(5) Weather resistance: Weather resistance was evaluated with a xenon weather meter (black panel temperature 63 ° C., 18 hours of rainfall during 2 hours of irradiation, 1000 hours under the condition of irradiation energy of 180 W / m ² ). confirmed).
The criteria for the determination in the various characteristics evaluations (1) to (5) are as follows.

When there is no problem with the shape compared to the initial stage; ○
Abnormalities such as swelling, shrinkage, dissolution, whitening, cracks, etc. are observed compared to the initial stage; ×
(Example 2)
100 parts of the polymer [1] obtained in Production Example 1, 20 parts of isobornyl acrylate, 1.2 parts of Irgacure 184 (manufactured by Ciba Specialty Chemicals), 0.6 part of Irgacure 819 (manufactured by Ciba Specialty Chemicals), Irganox 1010 (Ciba Specialty) (Chemicals) 1.2 parts were added, mixed thoroughly, and impregnated into 36 parts of glass fiber to obtain a curable composition for prepreg.

  Next, the obtained curable composition was irradiated with light for 30 seconds with a metal halide lamp (80 W / cm, irradiation distance 15 cm, belt speed 1.0 m / min) to obtain a sheet-like cured product having a thickness of about 2 mm. .

  In the same manner as in Example 1, the obtained cured product was evaluated for tensile properties, heat resistance, oil resistance, chemical resistance, water resistance and weather resistance. The results are shown in Table 1.

(Example 3)
100 parts of the polymer [1] obtained in Production Example 1, 30 parts of the polymer [2] obtained in Production Example 2, 1.3 parts of Nyper BW (75% by weight dibenzoyl peroxide, manufactured by NOF Corporation), Irganox 1010 (manufactured by Ciba Specialty Chemicals) 1.3 parts was added, mixed well, and impregnated into 39 parts of glass fiber to obtain a curable composition for prepreg.

  Next, the obtained curable composition was pressed at 180 ° C. for 15 minutes to obtain a sheet-like cured product having a thickness of about 2 mm.

  In the same manner as in Example 1, the obtained cured product was evaluated for tensile properties, heat resistance, oil resistance, chemical resistance, water resistance and weather resistance. The results are shown in Table 1.

(Comparative Example 1)
Except not using glass fiber, the hardened | cured material was adjusted with the method similar to Example 1, and hardened | cured material was obtained.

  In the same manner as in Example 1, the obtained cured product was evaluated for tensile properties, heat resistance, oil resistance, chemical resistance, water resistance and weather resistance. The results are shown in Table 1.

(Comparative Example 2)
Except not using glass fiber, the hardened | cured material was adjusted with the method similar to Example 3, and the hardened | cured material was obtained.

  In the same manner as in Example 1, the obtained cured product was evaluated for tensile properties, heat resistance, oil resistance, chemical resistance, water resistance and weather resistance. The results are shown in Table 1.

表１の結果から明らかなとおり、強化繊維を使用した実施例では、強化繊維を使用しなかった比較例と比べＴＢ（破断強度）が著しく向上しており、プリプレグとして有用なものであった。
以上のことから、本発明のプリプレグ用硬化性組成物から得られるプリプレグは、耐熱性、耐油性、耐候性、耐薬品性、耐水性に優れたプリプレグであることが分かる。

As is clear from the results in Table 1, in Examples using reinforcing fibers, TB (breaking strength) was remarkably improved as compared with Comparative Examples not using reinforcing fibers, which were useful as prepregs.
From the above, it can be seen that the prepreg obtained from the curable composition for prepreg of the present invention is a prepreg excellent in heat resistance, oil resistance, weather resistance, chemical resistance and water resistance.

Claims (25)

The following three components:
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, Ra 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 having one or more groups represented by the general formula (1) at the molecular terminals,
(B) an initiator, and
(C) A curable composition for a prepreg containing a reinforcing fiber as an essential component. The curable composition for prepreg according to claim 1, wherein the vinyl polymer of component (A) is a (meth) acrylic polymer. The component (A) is
To the vinyl polymer having a halogen group at the 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, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The curable composition for prepregs according to claim 1 or 2, which is produced by reacting the compound represented by formula (1). A vinyl polymer having a halogen group at the end is represented by the general formula (3):
-CR ¹ R ² X (3)
The prepreg according to claim 3 having a group represented by the formula: wherein R ¹ and R ² are groups bonded to an ethylenically unsaturated group of a vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom. Curable composition. The component (A) is
To the vinyl polymer having a hydroxyl group at the 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). Or the curable composition for prepregs of 2. The component (A) is
(1) A diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at a terminal,
(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 for prepregs according to claim 1 or 2. The curable composition for prepreg according to any one of claims 1 to 6, wherein the main chain of the component (A) is produced by living radical polymerization of a vinyl monomer. The curable composition for prepregs according to claim 7, wherein the living radical polymerization is atom transfer radical polymerization. The curable composition for prepreg according to claim 8, wherein the atom transfer radical polymerization is an organic halide or a sulfonyl halide compound as an initiator, and a transition metal complex selected from a complex of copper, nickel, ruthenium or iron is a catalyst. The curable composition for prepregs according to claim 9, wherein the transition metal complex is a copper complex. The curable composition for prepreg according to any one of claims 1 to 6, wherein the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent. The curable composition for prepregs according to any one of claims 1 to 11, wherein the number average molecular weight of the component (A) is 3000 or more. The vinyl polymer as the component (A) has a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography of less than 1.8, according to any one of claims 1 to 12. The curable composition for prepreg as described. Furthermore, the curable composition for prepregs in any one of Claims 1-13 which contains the monomer and / or oligomer which have a radically polymerizable group as (D) component. Furthermore, the curable composition for prepregs in any one of Claims 1-13 which contains the monomer and / or oligomer which have an anion polymerizable group as (D) component. (D) The curable composition for prepregs of Claim 14 or 15 containing the monomer and / or oligomer which have a (meth) acryloyl type group as a component. The curable composition for prepregs according to claim 16, further comprising a monomer and / or an oligomer having a (meth) acryloyl group as a component (D) and having a number average molecular weight of 5000 or less. The curable composition for prepreg according to any one of claims 1 to 17, wherein the initiator of the component (B) is a radical initiator. The initiator of (B) component is an anionic initiator, The curable composition for prepregs as described in any one of Claims 1-17. The curable composition for prepreg according to any one of claims 1 to 17, wherein the initiator of the component (B) is a redox initiator. The curable composition for prepreg according to any one of claims 1 to 20, wherein the component (C) is at least one selected from the group consisting of glass fiber, carbon fiber, and aramid fiber. object. A prepreg obtained by curing the curable composition for prepreg according to any one of claims 1 to 21. A prepreg obtained by irradiating the curable composition for a prepreg according to any one of claims 18, 19, and 21 with active energy rays. A prepreg obtained by heat-curing the curable composition for prepreg according to any one of claims 18, 19, and 21. A prepreg obtained by curing the curable composition for a prepreg according to claim 20 or 21 in a two-component system at room temperature.