JP4930967B2 - Unsaturated group-containing compound and composition thereof - Google Patents

Description

  The present invention relates to a novel unsaturated group-containing compound, and further includes a thermosetting resin composition containing the unsaturated group-containing compound and giving a cured product excellent in processability, adhesiveness, heat resistance and the like. About.

  Thermosetting resin compositions are used for various electrical insulating materials, structural materials, adhesives and the like as casting, impregnation, lamination, and molding materials. In recent years, the usage conditions of materials have become stricter in each of these applications, and in particular, the heat resistance of materials has become an important requirement.

  However, thermosetting polyimide resins generally used in thermosetting resin compositions have good heat resistance, but require high temperature and long time heating during processing, resulting in poor processability. It was. Moreover, although the epoxy resin which improved heat resistance is excellent in workability, its mechanical characteristics at high temperature, electrical characteristics, long-term heat deterioration resistance, and high heat resistance function were insufficient.

  Therefore, as alternative materials, for example, thermosetting resin mixtures containing polyimide and alkenylphenol or alkenylphenol ether, heat-resistant resin compositions containing maleimide compounds, polyallylic phenol compounds and epoxy resins have been proposed. Yes. (Patent Documents 1 and 2)

JP 05-43629 A JP 07-278268 A

  The present invention is a low-viscosity compound having an unsaturated double bond having a functionalizable hydroxyl group and can be used as a curable resin composition itself, and also serves as an intermediate for various functional compounds. To do.

（式中、ｎは０〜３の整数を示すが２個あるｎが同時に０となることはない。Ｐ、Ｒ及びＱはそれぞれ水素原子、炭素数１〜８のアルキル基またはアリール基のいずれかを表し、個々のＰ、Ｒ、Ｑはそれぞれ互いに同一であっても異なっていても良い。）で示されるポリアルケニル化合物、
（２）上記（１）に記載のポリアルケニル化合物及びマレイミド化合物を必須成分とする樹脂組成物、
（３）上記（２）に記載の樹脂組成物を硬化してなる硬化物
を、提供するものである。 That is, the present invention provides (1) the following formula (1)

(In the formula, n represents an integer of 0 to 3, but two n are not simultaneously 0. P, R, and Q are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group. Each of P, R, and Q may be the same or different from each other).
(2) A resin composition comprising the polyalkenyl compound and maleimide compound described in (1) as essential components,
(3) A cured product obtained by curing the resin composition according to (2) is provided.

  The polyalkenyl compound of the present invention is a compound having a hydroxyl group that can be easily made into a reactive functional group and having an unsaturated double bond, and can itself be used as a curable resin composition. The compound of the present invention can be used as an intermediate for various functional compounds.

（式中、ｍは１〜３の整数を表す。Ｒ及びＱは式（１）におけるのと同じ意味を表す。）
で表されるアリルフェノール類とエピハロヒドリンとの反応によって得られる。反応は、エピハロヒドリンに対し、過剰のアリルフェノール類を反応させる、もしくはアリルフェノール類の水酸基をグリシジルエーテル化した後、さらにアリルフェノール類と反応させる方法から選択できる。後者の場合、選択的に非対称型のポリアルケニル化合物を得ることができることから精密な分子設計をする意味で有効である。 The polyalkenyl compound of the present invention has the following formula (2):

(In the formula, m represents an integer of 1 to 3. R and Q have the same meaning as in formula (1).)
It is obtained by the reaction of allylphenols represented by the formula and epihalohydrin. The reaction can be selected from a method in which an excess of allylphenol is reacted with epihalohydrin, or after the hydroxyl group of allylphenol is glycidyl etherified and further reacted with allylphenol. In the latter case, an asymmetric polyalkenyl compound can be selectively obtained, which is effective in terms of precise molecular design.

The allylphenol to be used may be produced by the Claisen transition using allylphenol or an allyl ether of phenol as a raw material.
The phenols mentioned here include, in addition to phenol, halogen atoms, C1-C8 hydrocarbon groups, substituted phenols substituted with a trifluoromethyl group, and the like. Specifically, phenol o, m, It is a compound having each of the substituents described below independently at any one of p or two of five substitution positions. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Moreover, as a C1-C8 hydrocarbon group, a methyl group, an ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, cyclobutyl. Group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, n-octyl group, cyclooctyl group, etc. A chain alkyl group or a cyclic alkyl group, an allyl group or an aryl group. Examples of the aryl group include, but are not limited to, a phenyl group, a naphthyl group, and a toluyl group. Moreover, it can also be made to react by replacing a part of raw material allylphenols with phenols which do not have an allyl group. Examples of the phenols at this time include the aforementioned phenols.

  As a method for synthesizing the allyl ethers of the phenols, a known method is adopted, and for example, the method described in Patent Document 1 is used. For example, a phenol, an allyl halide, an alkylsulfonyl ether, or the like is reacted under basic conditions. Specific examples of the allyl compound herein include allyl bromide, allyl chloride, allyl iodide, methallyl bromide, methallyl chloride, methallyl iodide, allyloxymethane sulfonate, and allyloxytosylate. The obtained allyl ethers are heat-treated at a temperature of 160 to 250 ° C. and subjected to Claisen transition to obtain the desired allylphenols.

  The reaction of allylphenols with epihalohydrin is carried out by reacting in one stage (Method A) or two stages (Method B). In particular, when the purpose is to reduce the amount of impurities due to side reactions, the method B is preferably employed.

  The method A is a reaction in which two molecules of allylphenols are combined in one step using epihalohydrin as a linker. In Method A, an excess equivalent of allylphenol is reacted with epihalohydrin under basic conditions. In the reaction for obtaining the polyalkenyl compound of the present invention, an alkali metal hydroxide is preferred as the base. The alkali metal hydroxide may use the solid substance, and may use aqueous solution. The usage-amount of an alkali metal hydroxide is 0.9-2.5 mol normally with respect to 1 mol of epoxy groups of the epihalohydrin to be used, Preferably it is 0.95-2.0 mol.

  In this reaction, a quaternary ammonium salt may be added as a catalyst as necessary to facilitate the reaction. Examples of quaternary ammonium salts that can be used include tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride. The amount of the quaternary ammonium salt used is usually 0.1 to 15 parts by weight, preferably 0.2 to 10 parts by weight, based on 1 mol of the hydroxyl group of allylphenols.

  The usage-amount of epihalohydrin is 0.1-1.0 mol normally with respect to 1 mol of hydroxyl groups of allylphenol, Preferably it is 0.2-0.8 mol. Epihalohydrin used is epichlorohydrin derivatives such as epichlorohydrin α-methylepichlorohydrin, β-methylepichlorohydrin, γ-methylepichlorohydrin, epibulumhydrin, epiiodohydrin, etc. Industrially, epichlorohydrin derivatives are easy to use. In order to increase the solubility of allylphenols during the reaction and to carry out the reaction under mild conditions, alcohols such as methanol, ethanol, isopropyl alcohol, butanol and t-butanol, dimethyl sulfoxide, dimethylformamide, dimethyl sulfone, Aprotic polar solvents such as tetrahydrofuran, dioxane, 1,3-dimethyl-2-imidazolidinone, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, butyl lactate and propylene glycol monomethyl ether acetate It is preferable to carry out the reaction by adding a solvent such as aromatic compounds such as toluene and xylene.

  When a solvent is used, the amount used is usually 2 to 1000% by weight, preferably 5 to 300% by weight, based on the total weight of the raw materials.

  The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours.

  After completion of the reaction, the by-produced salt is removed by filtration, washing with water, and the polyalkenyl compound of the present invention can be obtained by distilling off unreacted raw materials, solvent and the like under heating and reduced pressure.

  Method B is a method in which allylphenols are reacted with an excess of epihalohydrin in the first step to form an epoxy compound, and then reacted with another molecule of allylphenols in the second step to obtain the target product.

  The reaction of allylphenols and epihalohydrin can be performed according to a conventionally known method. For example, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a mixture of allylphenols and epihalohydrin, or reacted at 20 to 120 ° C. for 0.5 to 10 hours while being added. At this time, the alkali metal hydroxide may be used in the form of an aqueous solution. In this case, the alkali metal hydroxide is continuously added and water and epihalohydrin are continuously added from the reaction mixture under reduced pressure or normal pressure. Distillation, liquid separation, removal of water, and epihalohydrin may be continuously returned to the reaction mixture. Examples of the epihalohydrin that can be used in this method include the same as those used in the method A.

  In said method, the usage-amount of epihalohydrin is 2.0-20 mol normally with respect to 1 mol of hydroxyl groups of allyl phenols, Preferably it is 3.0-10 mol. The usage-amount of an alkali metal hydroxide is 0.5-1.5 mol normally with respect to 1 mol of hydroxyl groups of allylphenol, Preferably it is 0.7-1.2 mol. At this time, side reactions can be suppressed by adding an aprotic solvent such as dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone. The amount of the aprotic polar solvent used is 5 to 200% by weight, preferably 10 to 100% by weight, based on the weight of the epihalohydrin. In addition to the above-mentioned solvent, the reaction can easily proceed by adding alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and t-butanol. Moreover, toluene, xylene, etc. can also be used.

  In this reaction, a quaternary ammonium salt may be added as a catalyst as necessary to facilitate the reaction. Examples of quaternary ammonium salts that can be used include tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride. The amount of the quaternary ammonium salt used is usually 0.1 to 15 parts by weight, preferably 0.2 to 10 parts by weight, based on 1 mol of the hydroxyl group of allylphenols.

  Alternatively, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is used as a catalyst in a mixture of allylphenols and excess epihalohydrin at 50 to 150 ° C. for 1 to 10 hours. The resulting halohydrin ether of allylphenol is added with a solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, and reacted again at 20 to 120 ° C. for 1 to 10 hours to react with halohydride. It is also possible to obtain an epoxidized product of allylphenols by ring closure of the phosphorus ether. The amount of the quaternary ammonium salt used in this case is usually 0.001 to 0.2 mol, preferably 0.05 to 0.1 mol, relative to 1 mol of the hydroxyl group of allylphenol. The usage-amount of an alkali metal hydroxide is 0.8-1.5 mol normally with respect to 1 equivalent of hydroxyl groups of allylphenol, Preferably it is 0.9-1.1 mol.

After completion of the reaction, by-product salts are removed by filtration, washing with water, etc., and an epoxidized product of allylphenols can be obtained by distilling off excess epihalohydrin and the like under heating and reduced pressure.
If a higher-purity epoxidized product is required, after the reaction is completed, the reaction product is washed with water, or after removing excess epihalohydrins and solvents under heating and reduced pressure without washing with water, and then again with toluene, methyl isobutyl ketone. Then, it is dissolved in a solvent such as methyl ethyl ketone and ethyl acetate, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to react again. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.2 mol, preferably 0.05 to 0.1 mol, per mol of hydroxyl group of allylphenol. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours. After completion of the reaction, the by-produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain a highly pure epoxidized allylphenol.

  Subsequently, the target polyalkenyl compound is obtained by reacting the resulting epoxidized product with allylphenols. This reaction is a technique commonly called fusion, and is non-catalytic or organic phosphines such as triphenylphosphine, tolylphenylphosphine, triphenylphosphine-hydroquinone complex, tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium The reaction can also be carried out using a catalyst such as a quaternary ammonium salt such as chloride, a solvent such as dimethylformamide or N-methylpyrrolidone, or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Although the amount of the catalyst used depends on the catalyst, it is usually 0.0001 to 0.2 mol, preferably 0.0005 to 0.1 mol, based on 1 mol of the hydroxyl group of allylphenols.

  The reaction may be solvent-free, but a solvent may be added separately in order to carry out the reaction under mild conditions. Specific examples of solvents that can be used include dimethylsulfoxide, dimethylformamide, dimethylsulfone, tetrahydrofuran, dioxane, aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like. Examples include, but are not limited to, ketones, ethyl acetate, butyl lactate, esters such as propylene glycol monomethyl ether acetate, and aromatic compounds such as toluene and xylene.

  The reaction temperature is usually 50 to 180 ° C., and the reaction time is usually 0.5 to 2 hours. After the completion of the reaction, the polyalkenyl compound of the present invention can be obtained by removing the catalyst by filtration, washing with water, etc., if necessary, and further distilling off the solvent and the like under heating and reduced pressure as necessary.

The polyalkenyl compound of the present invention thus obtained has two types of functional groups, an unsaturated double bond and a hydroxyl group, and is therefore useful as various synthetic intermediates.
For example, by reacting with phenols in the presence of an acid catalyst, an oligomer similar to phenol novolac can be produced. Moreover, an epoxy compound can be synthesized by oxidizing the allyl group with a peroxide or halohydrin and then ring-closing with a base, and a styrene derivative can be obtained by treating with a base. Furthermore, by photopolymerizing the central hydroxyl group (for example, an isocyanate compound having a (meth) acrylate group or an isocyanate compound having a maleimide group, specifically, Karenz MOI, Karenz AOI, etc.) It is also possible to form a compound having a functional site simultaneously in one molecule and to form a new curing system. Similarly, an epoxy resin having a carboxyl group and an epoxy group simultaneously in one molecule by reacting an acid anhydride with a hydroxyl group. It can also be. It can also act as a dienophile for the Dials-Alder reaction, and can also be reacted as an ene for the ene reaction. It is also possible to use a hydroxyl group and connect it with a diisocyanate to obtain a polyfunctional allyl compound. By using a hydroxyl group, it can be used as a branch of a dendrimer having an allyl group at the terminal.

  The polyalkenyl compound of the present invention is useful as a crosslinking agent in various polymer synthesis reactions. For example, it is known that a cured resin having excellent heat resistance and mechanical properties can be obtained by reacting a polymaleimide compound and a polyalkenyl compound.

  Here, the thermosetting resin composition containing the polyalkenyl compound of the present invention will be described in detail. By reacting the polymaleimide compound and the polyalkenyl compound, a cured resin product having excellent heat resistance and mechanical properties can be obtained. The polymaleimide compound used in the thermosetting resin composition of the present invention is a substance that is already widely known and used, and is not particularly limited as long as it has two or more maleimide groups in the molecule. .

  Specific examples of preferable polymaleimide compounds include bis (4-maleimidophenyl) methane, 1,2-dimaleimidobenzene, bis (3-maleimidophenyl) methane, 1,3-dimaleimidobenzene, and bis (4- Maleimidophenyl) ether, 1,4-dimaleimidobenzene, bis (3-maleimidophenyl) ether, 1,4-dimaleimidonaphthalene, 2,3-dimaleimidonaphthalene, 1,5-dimaleimidonaphthalene, 4,4 ′ -Dimaleimidobiphenyl, 1,8-dimaleimidonaphthalene, 3,3'-dimaleimidobiphenyl, 2,6-dimaleimidonaphthalene, 3,4'-dimaleimidobiphenyl, 2,7-dimaleimidonaphthalene, 2,2 '-Bis [4- (4-maleimidophenyloxy) phenyl] sulfone 2,5-dimaleimido-1,3-xylene, bis (4-maleimidophenyl) ketone, bis (4-maleimidophenyl) sulfone, 1,5-dimaleimidoanthraquinone, bis (3-maleimidophenyl) sulfone, 1,2 -Dimaleimidoanthraquinone, 2,7-dimaleimidofluorene, 9,9-bis (4-maleimidophenyl) fluorene, 3,7-dimaleimido-2-methoxyfluorene, 9,9-bis (4-maleimido-3-methyl) Phenyl) fluorene, 9,10-dimaleimidophenanthrene, 9,9-bis (3-ethyl-4-maleimidophenyl) fluorene, 3,6-dimaleimide acridine, 1,2-dimaleimide anthraquinone, 1,5-dimaleimide anthraquinone 2,6-dimaleimide anthraquinone, 3, 8-dimaleimido-6-phenylphenanthridine, bis (4-maleimidocyclohexyl) methane, bis (3-maleimidocyclohexyl) methane, 1,1,1,3,3,3-hexafluoro-2,2-bis [ 4- (4-maleimidophenyloxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-maleimidophenyl) propane, 1,4-bis (4-maleimide) Phenyl) benzene, 1,4-bis (4-maleimidophenyl) cyclohexane, bis (4-maleimidophenyl) diphenylsilane, bis (4-maleimidophenyl) sulfide, bis (3-maleimidophenyl) sulfide, bis (4-maleimide) Phenyl) sulfoxide, bis (3-maleimidophenyl) sulfoxide, 2,2-biphenyl (4-maleimidophenyl) propane, 2,2-bis [4- (4-maleimidophenyloxy) phenyl] propane, bis (3-methyl-4-maleimidophenyl) methane, bis (3,5-dimethyl-4- Maleimidophenyl) methane, isophorone dimaleimide, 1,2-dimaleimidoethane, 1,4-dimaleimidobutane, 1,6-dimaleimidohexane, 1,3-bis (maleimidomethyl) cyclohexane, 1,4-dimaleimide- 2-butanone, 1,2-dimaleimidocyclohexane, 1,10-dimaleimidodecane, 1,12-dimaleimidodecane, 1,7-dimaleimidoheptane, 2,5-dimaleimidopyridine, 1,3-dimaleimide- 2-hydroxypropane, 1,8-dimaleimide-p-menthane, 2,3-dimaleimide Phthalene, 1,2-dimaleimido-2-methylpropane, 1,9-dimaleimidononane, 1,8-dimaleimidooctane, 1,5-dimaleimidopentane, 1,3-dimaleimidopropane, 2,4 dimaleimide Phenol, 3,4-dimaleimidobenzophenone, 2,6-dimaleimidotoluene, 3,4-dimaleimidotoluene, adamantane-1,3-dimaleimide, 2,3-dimaleimidopyridine, 1,4-bis (3- Maleimidopropyl) piperazine, 4,5-dimaleimidopyridine 2,6-dimaleimidopyridine, 3,4-dimaleimidopyridine bis (3-ethyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4- Maleimidophenyl) methane, bis (3-propyl-4-maleimidophenyl) methane, bis (3 5-dipropyl-4-maleimidophenyl) methane, bis (3-butyl-4-maleimidophenyl) methane, bis (3,5-dibutyl-4-maleimidophenyl) methane, 2-methyl-1,4-dimaleimidobenzene 2,3-dimethyl-1,4-dimaleimidobenzene, 2,5-dimethyl-1,4-dimaleimidobenzene, 2,6-dimethyl-1,4-dimaleimidobenzene, 4-ethyl-1,3 Dimaleimidobenzene, 5-ethyl-1,3-dimaleimidobenzene, 4,6-dimethyl-1,3-dimaleimidobenzene, 2,4,6-trimethyl-1,3-dimaleimidobenzene, 2,3 , 5,6-tetramethyl-1,4-dimaleimidobenzene, bis (3-ethyl-4-maleimido-5-methylphenyl) methane, 4-methyl-1,3 Bismaleimide such as dimaleimidobenzene; trismaleimide such as tris (4-maleimidophenyl) methane; tetrakismaleimide such as bis (3,4-dimaleimidophenyl) methane; poly (4-maleimidostyrene) and poly (3-maleimide) Styrene) and polymaleimide compounds obtained by maleimidizing aromatic polyamines such as aniline resins obtained by the reaction of aniline and formaldehyde.

  The composition of this invention should just adjust a composition according to the required performance and use of a polyalkenyl compound and a polymaleimide compound, and usually makes a molar ratio (polyalkenyl compound / polymaleimide compound) 0.05-20. The range is preferably from 0.1 to 5, more preferably from 0.5 to 2.

The following components can be added to the thermosetting resin composition of the present invention as necessary.
(A) Alkenyl phenyl ether: an ether in which an alkenyl group and a benzene ring are bonded via oxygen, and preferred specific examples include the following compounds. That is, 4,4′-bis (2-methyl-2-propenyloxy) biphenyl, bis [4- (2-methyl-2-propenyloxy) phenyl] sulfoxide, bis [4- (2-methyl-2-propenyl) Oxy) phenyl] sulfide, bis [4- (2-methyl-2-propenyloxy) phenyl] ether, bis [4- (2-methyl-2-propenyloxy) phenyl] ketone, 9,9-bis [4- (2-methyl-2-propenyloxy) phenyl] fluorene, 1,1-bis [4- (2-propenyloxy) phenyl] ethylbenzene, 1,1-bis [4- (2-propenyloxy) phenyl] cyclohexane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (2-propenyloxy) phenyl] propane, bis [4- (2- Lopenyloxy) phenyl] ketone, 9,9-bis [4- (2-propenyloxy) phenyl] fluorene, 1,4-bis (2-propenyloxy) benzene, 1,2,4-tris (2-propenyloxy) Benzene, 2,3-bis (2-methyl-2-propenyloxy) benzaldehyde, 2,4-bis (2-methyl-2-propenyloxy) benzaldehyde, 2,5-bis (2-methyl-2-propenyloxy) ) Benzaldehyde, 3,4-bis (2-methyl-2-propenyloxy) benzaldehyde, 1,1,1-tris [4- (2-methyl-2-propenyloxy) phenyl] ethane, 1- [1-methyl -1- (4- (2-methyl-2-propenyloxy) phenyl) ethyl, 4- [1,1-bis (4- (2-methyl-2-prop Penyloxy) phenyl) ethyl] benzene, 1- [1-methyl-1- (4- (2-propenyloxy) phenyl) ethyl-4- [1,1-bis (4- (2-propenyloxy) phenyl) ethyl Benzene, 2,3-bis (2-propenyloxy) benzaldehyde, 2,4-bis (2-propenyloxy) benzaldehyde, 2,5-bis (2-propenyloxy) benzaldehyde, 3,4-bis (2- Propenyloxy) benzaldehyde, 1,1,1-tris [4- (2-propenyloxy) phenyl] ethane, 1- [1-methyl-1- (4- (2-propenyloxy) phenyl) ethyl] -4- And [1,1-bis (4- (2-propenyloxy) phenyl) ethyl] benzene. Among these, alkenyl phenyl ether having two methallyl groups or allyl groups is a preferred compound. The preferred amount of alkenyl phenyl ether added varies depending on the application, but is up to 50% by weight based on the total amount of the resin composition.

  (B) Alkenylphenol: Phenol in which an alkenyl group is bonded to a benzene ring, and preferred specific examples include the following compounds. 3,3′-bis (2-methyl-2-propenyl) -4,4′-biphenyldiol, 3,3′-bis (2-methyl-2-propenyl) -2,2′-biphenyldiol, 3,3′-di (2-propenyl) -4,4′-biphenyldiol, 3,3′-di (2-propenyl) -4,4′-biphenyldiol, 2,2′-bis [4-hydroxy -3- (2-methyl-2-propenyl) phenyl] propane, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] methane, bis [4-hydroxy-3- (2-methyl-) 2-propenyl) phenyl] sulfoxide, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] sulfide, bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] ate Bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] sulfone, 2,2-bis [4-hydroxy-3- (2-propenyl) phenyl] propane, bis [4-hydroxy-3 -(2-propenyl) phenyl] methane, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfoxide, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfide, bis [4-hydroxy- 3- (2-propenyl) phenyl] ether, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfone, 1,1-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl ] Ethylbenzene, 1,1-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] cyclohexane, 1,1,1 3,3,3-hexafluoro-2,2-bis - [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane, and the like. Among these, preferred compounds are alkenylphenols having two methallyl groups. Although the preferable addition amount of these alkenyl phenols changes with uses, it exists to 50 weight% with respect to the total amount of a resin composition.

  (C) Epoxy resin: an epoxy compound having at least two epoxy groups in one molecule. Examples thereof include novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, and triphenylmethane type epoxy resins. Specifically, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1 , 1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetofu Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols Solid or liquid epoxy resins such as chemical compounds, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins and the like are not limited thereto. These may be used alone or in combination of two or more. Although the preferable addition amount of these epoxy resins changes with uses, it exists to 50 weight% with respect to the total amount of a resin composition.

(D) Epoxy resin curing agent: a curing agent for epoxy resin, an effective component for blending an epoxy resin in the composition, and any known curing agent for epoxy resin should be used. it can. Preferable epoxy resin curing agents include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and the like. Curing agents that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophorone diamine, dicyandiamide, polyamide resin synthesized from ethylene diamine, phthalic anhydride, trimellitic anhydride, anhydrous Pyromellitic acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene Phenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol Hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy Benzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl)- 1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis And polycondensates with methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine complexes, guanidine derivatives, and condensates of terpenes and phenols. However, it is not limited to these. These may be used singly or in combination of two or more, preferably phenolic compounds and amine compounds, more preferably phenolic compounds. In particular, amine compounds are also effective as maleimide curing agents. Although the preferable addition amount of these epoxy resin hardening | curing agents changes with uses, it exists to 50 weight% with respect to the total amount of a resin composition.

(E) Radical initiator: A radical initiator for heat-curing the composition. The composition of the present invention is easily cured even in the absence of a curing reaction initiator, but in some cases, a radical initiator can also be used. Preferred examples include cumyl peroxide, tert-butyl peroxide, acetyl peroxide, propionyl peroxide, benzoyl peroxide, 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl oxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroxyperoxide, pertriphenylacetic acid tert-butyl, tert-butyl peracetate, tert-butyl hydroperoxide, tert-butyl perbenzoate, tert-butyl performate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, per-N- (3 -Toluyl) peroxides such as tert-butyl carbamate; 2,2'- Zobispropane, 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo (methylethyl) diacetate, 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2 ' -Azobis (2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile, 2,2'-azobisisobuty Mixture of 21.5 parts by weight of stannic chloride per 1 part by weight of nitrile, methyl 2,2′-azobis-2-methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2 ′ A mixture of 19.53 parts by weight of stannic chloride per 1 part by weight of azobis-2-methylbutyronitrile, 2,2′-dimethyl azobisisobutyrate, dimethyl 2,2′-azobisisobutyrate, 1,1′-azo (1-methylbutyronitrile-3-sodium sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4′-azobis-4-cyanovaleric acid, 3,5- Dihydroxymethylphenylazo-2-methylmalonodinitrile, 2,2′-azobis-2-methylvaleronitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 4,4-azobis-4- Dimethyl cyanovalerate, 2,2, -azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'-azobis -1-chlorophenylethane, 1,1′-azobis-1-cyclohexanecarbonitrile, 1,1′-azobis-1-phenylethane, 1,1′-azo Scumene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1′-azobis-1,2-diphenylmethane, poly (bisphenol A-4 , 4′-azobis-4-cyanopentaate) and poly (tetraethylene glycol-2,2′-azobisisobutyrate) and the like; 1,4-bis (pentaethylene1-2-tetrazene, benzene Examples include sulfonyl azide and 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazene. The preferred addition amount of these radical initiators is up to 5% by weight based on the total amount of the whole composition, depending on the application.

(F) Inorganic filler: It is added to improve the cured product properties such as mechanical properties. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. Although the preferable addition amount of these inorganic fillers changes with uses, it exists to 95 weight% with respect to the total amount of a resin composition. Furthermore, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added to the curable resin composition of the present invention. can do.

  (G) Flame retardant: A component for imparting flame retardancy to the cured resin. Preferred examples include the following. That is, tetrabromobisphenol A dimethacrylate reaction product, tetrabromobisphenol A, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, 2,2-bis (4-hydroxyethoxy-3,5-dibromophenyl) ) Brominated flame retardants such as propane and decabromodiphenyl ether, inorganic flame retardants such as antimony trichloride, zirconium hydroxide, magnesium hydroxide, tin oxide, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, Aromatic phosphate ester flame retardants such as zirdiphenyl phosphate, phenylene bis (phenyl cresyl phosphate), xylenyl diphenyl phosphate, phenylene bis (dicresyl phosphate) and their polycondensates, tris (2-c Roechiru) phosphate, bis (2-chloroethyl) such as vinyl phosphate (halo) alkyl phosphate flame retardant and a polycondensate and red phosphorus inorganic phosphorus flame retardants, etc., and the like. Although the preferable addition amount of these flame retardants changes with uses, it exists to 50 weight% with respect to the total amount of a resin composition.

  (H) Synthetic resin: A component for imparting various properties to the cured resin. Preferable specific examples include the following. That is, synthetic resins such as phenol resin, alkyd resin, melamine resin, fluororesin, vinyl chloride resin, acrylic resin, silicone resin, butadiene rubber, butadiene acrylonitrile rubber, and polyester resin can be used. Although the preferable addition amount of these synthetic resins changes with uses, it exists to 50 weight% with respect to the total amount of a resin composition.

  The resin composition of the present invention can be easily prepared by uniformly mixing each of the above components at a temperature that does not reach the curing temperature of the composition, and this can be performed at an appropriate temperature, for example, 120 to 300 ° C. By heating for ˜20 hours, it can be easily cured and a cured product having excellent heat resistance and mechanical properties can be obtained.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified.

Example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 134 parts of 2-allylphenol, 555 parts of epichlorohydrin, and 56 parts of methanol, and the temperature was raised to 70 ° C. with stirring. Next, 40 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then stirred at 70 degrees for 1 hour. After completion of the reaction, 150 parts of water was added and washed twice with water to remove the generated salt and the like, and then excess epichlorohydrin and the like were distilled off under heating and reduced pressure. To the obtained residue, 300 parts of methyl isobutyl ketone was added and dissolved, and the system was kept at 70 ° C. 10 parts of 30% aqueous sodium hydroxide solution was added thereto, heated for 1 hour, and then washed with 200 parts of water three times. The obtained organic layer was concentrated under heating and reduced pressure to obtain 187 parts of 2-glycidyloxyallylbenzene as a liquid compound. The epoxy equivalent of the obtained compound was 194 g / eq. Met.
Furthermore, 97 parts of the epoxy compound obtained in a flask equipped with a stirrer, a reflux condenser, and a stirrer, 67 parts of 2-allylphenol, 30 parts of methyl ethyl ketone and 2 parts of tetramethylammonium chloride were charged, and the mixture was stirred up to 100 ° C. The temperature was raised and the mixture was heated as it was for 10 hours, and then 300 parts of methyl isobutyl ketone was added, followed by washing with 200 parts of water three times. The obtained organic layer was concentrated under heating and reduced pressure to obtain 161 parts of the desired polyalkenyl compound of the present invention as a liquid compound. The viscosity of the obtained compound was 111 mPa · s (E-type viscometer), and no epoxy group was detected. The purity of the target product by GPC was 94%.

Example 2
65 parts of the polyalkenyl compound of the present invention obtained in Example 1 and 72 parts of 4,4-bis (maleimidophenyl) methane (manufactured by Tokyo Chemical Industry Co., Ltd.) are heated and melted at 120 ° C. and uniform, and then 150 ° C. For 5 hours, at 180 ° C. for 4 hours, and at 200 ° C. for 1 hour. It was 129 degreeC when the glass transition temperature was measured for the obtained hardened | cured material using TMA (thermomechanical measuring apparatus).

Claims (3)

Following formula (1)

(Wherein, n shows the integer 1 to 3. P, Q and R are each a hydrogen atom, or an alkyl or aryl group having 1 to 8 carbon atoms, each of P, R, Q is Each of which may be the same or different from each other). Polyalkenyl compound and polymaleimide compound a resin composition as an essential component of claim 1. A cured product obtained by curing the resin composition according to claim 2.