JP2007091857A - New compound and thermosetting resin composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound capable of imparting a thermosetting resin with high toughness while maintaining both of the flexural strength and flexural modulus inherent in the thermosetting resin, and to provide a thermosetting resin composition containing the above compound. <P>SOLUTION: The compound is represented by formula(1) or formula(2)[ wherein, R<SP>1</SP>is (substituted) phenyl, cyclohexyl or 1-6C alkyl; R<SP>2</SP>is -(CH<SB>2</SB>CH<SB>2</SB>O)<SB>p</SB>R<SP>4</SP>, wherein p is an integer of 1-150, R<SP>4</SP>is (substituted) phenyl, cyclohexyl or 1-6C alkyl; R<SP>3</SP>is H or methyl; and ratio(n/m) is (1,000:1) to (80:20) ]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel compound and a thermosetting resin composition using the same.

A prepreg obtained by impregnating carbon fiber with an epoxy resin is known as an aircraft structural material. The resin used for this prepreg usually requires high toughness.
Examples of the method for toughening the epoxy resin include (A) improvement of the resin and curing agent, and (B) improvement by addition of a modifier. The above (A) is intended to improve the toughness of the matrix resin skeleton and molecular chain. The above (B) is a method of toughening by adding a flexible polymer (for example, rubber or elastomer) or a tough thermoplastic polymer (for example, engineering plastic) to the resin system.

  To date, the inventors have added toughness by adding a terpolymer composed of N-phenylmaleimide, N-cyclohexylmaleimide, and styrene, or a binary copolymer composed of N-phenylmaleimide and styrene to an epoxy resin. Has been reported (see Patent Documents 1 to 3).

JP-A-5-306359 Japanese Patent Laid-Open No. 5-311028 JP 7-133393 A

  However, when the terpolymers or binary copolymers described in Patent Documents 1 to 3 are added to the epoxy resin, the toughness is improved, but the bending strength and the bending elastic modulus tend to decrease. Moreover, in applications that require higher performance, such as advanced technologies such as aerospace materials and electrical / electronic materials, resin compositions having better toughness are desired.

  Therefore, an object of the present invention is to provide a compound capable of imparting excellent toughness while maintaining the bending strength and bending elastic modulus of the thermosetting resin. Another object of the present invention is to provide a thermosetting resin composition containing this compound.

  The present inventor has found that when a new compound is synthesized and a specific amount of this compound is added to the thermosetting resin, excellent toughness can be imparted while maintaining the bending strength and flexural modulus of the thermosetting resin. The present invention has been completed.

（式中、Ｒ¹は、フェニル基、置換フェニル基、シクロへキシル基および炭素数１〜６のアルキル基のいずれかであり、
Ｒ²は、−（ＣＨ₂ＣＨ₂Ｏ）_pＲ⁴であり、ｐは、１〜１５０の整数であり、Ｒ⁴は、フェニル基、置換フェニル基、シクロへキシル基および炭素数１〜６のアルキル基のいずれかであり、
Ｒ³は、水素原子またはメチル基であり、
ｎとｍとの比（ｎ／ｍ）は、１０００／１〜８０／２０である。）
（２）重量平均分子量が５，０００〜７００，０００である上記（１）に記載の化合物。
（３）エポキシ樹脂、シアネート樹脂およびビスマレイミド樹脂からなる群から選択される少なくとも１種の熱硬化性樹脂と、
上記（１）または（２）に記載の、前記式（１）で表される化合物および／または前記式（２）で表される化合物とを含有し、
前記式（１）で表される化合物および／または前記式（２）で表される化合物の含有量が、前記熱硬化性樹脂１００質量部に対して１〜３０質量部である熱硬化性樹脂組成物。
（４）エポキシ樹脂、シアネート樹脂およびビスマレイミド樹脂からなる群から選択される少なくとも１種の熱硬化性樹脂と、下記式（３）で表される単量体、下記式（４）で表される単量体および下記式（５）で表される単量体と、重合開始剤とを混合し、
前記熱硬化性樹脂中で、下記式（３）で表される単量体、下記式（４）で表される単量体および下記式（５）で表される単量体を共重合して、前記式（１）で表される化合物を生成させて得られる、上記（３）に記載の熱硬化性樹脂組成物。

（式中、Ｒ¹は、フェニル基、置換フェニル基、シクロへキシル基および炭素数１〜６のアルキル基のいずれかであり、
Ｒ²は、−（ＣＨ₂ＣＨ₂Ｏ）_pＲ⁴であり、ｐは、１〜１５０の整数であり、Ｒ⁴は、フェニル基、置換フェニル基、シクロへキシル基および炭素数１〜６のアルキル基のいずれかである。）
（５）エポキシ樹脂、シアネート樹脂およびビスマレイミド樹脂からなる群から選択される少なくとも１種の熱硬化性樹脂と、下記式（３）で表される単量体、下記式（４）で表される単量体および下記式（６）で表される単量体と、重合開始剤とを混合し、
前記熱硬化性樹脂中で、下記式（３）で表される単量体、下記式（４）で表される単量体および下記式（６）で表される単量体を共重合して、前記式（２）で表される化合物を生成させて得られる、上記（３）に記載の熱硬化性樹脂組成物。

（式中、Ｒ¹は、フェニル基、置換フェニル基、シクロへキシル基および炭素数１〜６のアルキル基のいずれかであり、
Ｒ²は、−（ＣＨ₂ＣＨ₂Ｏ）_pＲ⁴であり、ｐは、１〜１５０の整数であり、Ｒ⁴は、フェニル基、置換フェニル基、シクロへキシル基および炭素数１〜６のアルキル基のいずれかであり、
Ｒ³は、水素原子またはメチル基である。） That is, the present invention provides the following (1) to (5).
(1) A compound represented by the following formula (1) or (2).

(In the formula, R ¹ is any ^one of a phenyl group, a substituted phenyl group, a cyclohexyl group, and an alkyl group having 1 to 6 carbon atoms;
R ² is — (CH ₂ CH ₂ O) _p R ⁴ , p is an integer of 1 to 150, R ⁴ is a phenyl group, a substituted phenyl group, a cyclohexyl group, and a carbon number of 1 to 6. Any of the alkyl groups of
R ³ is a hydrogen atom or a methyl group,
The ratio of n to m (n / m) is 1000/1 to 80/20. )
(2) The compound according to (1) above, wherein the weight average molecular weight is 5,000 to 700,000.
(3) at least one thermosetting resin selected from the group consisting of epoxy resins, cyanate resins and bismaleimide resins;
Containing the compound represented by the formula (1) and / or the compound represented by the formula (2) according to the above (1) or (2),
The thermosetting resin whose content of the compound represented by said Formula (1) and / or the compound represented by said Formula (2) is 1-30 mass parts with respect to 100 mass parts of said thermosetting resins. Composition.
(4) At least one thermosetting resin selected from the group consisting of epoxy resin, cyanate resin and bismaleimide resin, a monomer represented by the following formula (3), and represented by the following formula (4) A monomer represented by the following formula (5) and a polymerization initiator,
In the thermosetting resin, a monomer represented by the following formula (3), a monomer represented by the following formula (4), and a monomer represented by the following formula (5) are copolymerized. And the thermosetting resin composition as described in said (3) obtained by producing | generating the compound represented by said Formula (1).

(In the formula, R ¹ is any ^one of a phenyl group, a substituted phenyl group, a cyclohexyl group, and an alkyl group having 1 to 6 carbon atoms;
R ² is — (CH ₂ CH ₂ O) _p R ⁴ , p is an integer of 1 to 150, R ⁴ is a phenyl group, a substituted phenyl group, a cyclohexyl group, and a carbon number of 1 to 6. Any one of the alkyl groups. )
(5) At least one thermosetting resin selected from the group consisting of epoxy resin, cyanate resin and bismaleimide resin, a monomer represented by the following formula (3), and represented by the following formula (4) A monomer represented by the following formula (6) and a polymerization initiator,
In the thermosetting resin, a monomer represented by the following formula (3), a monomer represented by the following formula (4), and a monomer represented by the following formula (6) are copolymerized. The thermosetting resin composition according to (3), which is obtained by generating the compound represented by the formula (2).

(In the formula, R ¹ is any ^one of a phenyl group, a substituted phenyl group, a cyclohexyl group, and an alkyl group having 1 to 6 carbon atoms;
R ² is — (CH ₂ CH ₂ O) _p R ⁴ , p is an integer of 1 to 150, R ⁴ is a phenyl group, a substituted phenyl group, a cyclohexyl group, and a carbon number of 1 to 6. Any of the alkyl groups of
R ³ is a hydrogen atom or a methyl group. )

The compound of the present invention can impart excellent toughness while maintaining the bending strength and bending elastic modulus of the thermosetting resin.
Moreover, the composition of this invention can obtain the hardened | cured material which is excellent in bending strength and a bending elastic modulus, and especially excellent in toughness.

Hereinafter, the present invention will be described in more detail.
The compound of the present invention is a compound (block copolymer) represented by the following formula (1) or (2). More specifically, the compound represented by the following formula (1) is composed of a block composed of a repeating unit represented by the following formula (A) and a block composed of a repeating unit represented by the following formula (B). Is a block copolymer. The compound represented by the following formula (2) is a block copolymer comprising a block composed of a repeating unit represented by the following formula (A) and a block composed of a repeating unit represented by the following formula (C). is there.

In the above formula, R ¹ is a phenyl group, a substituted phenyl group, or a hexyl group and an alkyl group having 1 to 6 carbon atoms cyclohexylene.
The substituted phenyl group is a phenyl group substituted with at least one substituent selected from the group consisting of an alkyl group having 4 or less carbon atoms, a cyano group, a methoxy group, and a halogen.
Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Of these, a methyl group, an ethyl group, and a propyl group are preferable.
R ¹ is preferably a phenyl group or a substituted phenyl group from the viewpoint of excellent heat resistance and compatibility with a resin.

R ² is — (CH ₂ CH ₂ O) _p R ⁴ .
p is an integer of 1-150. In particular, p is preferably an integer of 10 to 60, considering the balance between the compatibility with the polyether chain and the water resistance.
R ⁴ is any one of a phenyl group, a substituted phenyl group, a cyclohexyl group, and an alkyl group having 1 to 6 carbon atoms. Specific examples of the substituted phenyl group and the alkyl group having 1 to 6 carbon atoms are the same as those described for R ¹ above. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, from the viewpoint of compatibility, control of phase structure after thermosetting, and balance of bending characteristics.

R ³ is a hydrogen atom or a methyl group, and a methyl group is preferable from the viewpoint of ease of polymer synthesis.
The ratio of n to m (n / m) is 1000/1 to 80/20. n is an integer of 4 or more, preferably an integer of 80 to 1000, and m is an integer of 1 or more, preferably an integer of 1 to 20.

The weight average molecular weight of the compound represented by the above formula (1) and the compound represented by the formula (2) is preferably 5,000 to 700,000, and preferably 10,000 to 500,000. More preferred. When the weight average molecular weight is within this range, the low viscosity of the uncured resin can be maintained, so that workability is excellent.
In addition, the weight average molecular weight in this specification is a standard polystyrene conversion value by a gel permeation chromatography method.

The glass transition temperature of the compound represented by formula (1) and the compound represented by formula (2) (T _g) is preferably from 190 to 240 ° C.. When the glass transition temperature is within this range, when it is added to a thermosetting resin to form a composition, a decrease in physical properties of the cured product at a low temperature (about −100 to 130 ° C.) can be suppressed. T _g is not greatly affected. Therefore, it is suitably used particularly for aircraft materials.
In addition, the glass transition temperature in this specification is the temperature measured by differential scanning calorimetry (DSC).

  The compound of the present invention represented by the above formula (1) is obtained by mixing a monomer represented by the following formulas (3) to (5) and a polymerization initiator in an organic solvent such as acetone. The reaction can be carried out at about 60 to 80 ° C. for 6 to 10 hours to copolymerize the above monomers.

  The method for producing the compound of the present invention represented by the above formula (2) is based on the above formula, except that the monomer to be used is a monomer represented by the following formula (3), (4) and (6). This is the same as the method for producing the compound of the present invention represented by (1).

In the formulas (3) to (6), R ¹ , R ² and R ³ are the same as those in the above formulas (1) to (2).

  The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. Specifically, for example, an azo compound such as 2,2′-azobisisobutyronitrile (AIBN), Examples include peroxides such as benzoyl peroxide and dicumyl peroxide (DICUP).

  As another method for producing the compound of the present invention, the thermosetting resin, the monomer, and the polymerization initiator are mixed and thermoset as in the method for producing the composition of the present invention described later. The method for producing the compound of the present invention by copolymerizing the above monomers in a functional resin reduces VOC, shortens the work process, improves the workability during production and use of the composition due to reduced viscosity, etc. Preferably mentioned from a point.

When the compound of the present invention is produced by mixing the thermosetting resin, the monomer, and the polymerization initiator and copolymerizing the monomer in the thermosetting resin, In addition to the body, monomers such as divinyl compounds, diacrylates or triacrylates may be added and copolymerized in amounts that do not impair the effects of the present invention. The compounds of the present invention obtained by adding monomers such as divinyl compounds, diacrylates or triacrylates are also excellent in heat resistance and solvent resistance.
Specific examples of the divinyl compound include divinylbenzene. Specific examples of the diacrylates include neopentyl glycol dimethacrylate and the like. Specific examples of the triacrylates include trimethylolpropane triacrylate and isocyanuric acid-modified triacrylate.

Hereinafter, the thermosetting resin composition of the present invention will be described in detail.
The thermosetting resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) includes at least one thermosetting resin selected from the group consisting of epoxy resins, cyanate resins, and bismaleimide resins. A compound represented by the above formula (1) and / or a compound represented by the above formula (2), and a compound represented by the above formula (1) and / or the above formula (2). Is a thermosetting resin composition whose content of the compound represented by is 1-30 mass parts with respect to 100 mass parts of the said thermosetting resins.

Content of the compound represented by the said Formula (1) and / or the compound represented by the said Formula (2) is 1-30 mass parts with respect to 100 mass parts of said thermosetting resins. If content is this range, the bending strength and bending elastic modulus of the hardened | cured material of the composition obtained can be maintained, and toughness can be improved. The content of the compound represented by the above formula (1) and / or the compound represented by the above formula (2) is such that the thermosetting property of the compound represented by the above formula (1) is obtained from the point that a cured product having these characteristics aligned in a higher dimension can be obtained. 5-20 mass parts is preferable with respect to 100 mass parts of resin.
In addition, the said content is content of the sum total of these, when the composition of this invention contains both the compound represented by the said Formula (1), and the compound represented by the said Formula (2). Yes, when only one of the compounds is contained, it is the content.

  The epoxy resin used in the composition of the present invention is a compound having at least one epoxy group, and is not particularly limited. Specifically, for example, bisphenol A type epoxy resin obtained by the reaction of bisphenol A and epichlorohydrin, brominated epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, cycloaliphatic epoxy resin, Examples thereof include various epoxy resins such as glycidyl isocyanurate (TGIC), bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and modified epoxy resins thereof. These may be used alone or in combination of two or more.

  Moreover, it is preferable that the said epoxy resin has at least 1 aromatic ring from the point which is excellent in the mechanical strength and heat resistance of hardened | cured material. In particular, bisphenol A type epoxy resin, cresol novolac type epoxy resin, tetraglycidyl diaminodiphenylmethane (TGDDM), dicyclopentadienyl type epoxy resin, triglycidyl paraaminophenol, and triglycidyl metaaminophenol are excellent in workability, heat resistance and water resistance. It is preferable because of its excellent properties.

  The epoxy equivalent of the said epoxy resin is not specifically limited, According to a use, it can select suitably. Preferably it is about 100-1000, More preferably, it is about 100-500. When the epoxy equivalent is within this range, mixing with the above-described compound of the present invention is facilitated, and the epoxy resin can be toughened more effectively.

The cyanate resin used in the composition of the present invention is not particularly limited as long as it is a compound having a cyanate group (—OCN) at the terminal. Specifically, for example, 1,1′-bis (4-cyanatophenyl) is used. ) Ethane, bis (4-cyanato-3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatophenyl-1- (1-methylethylidene)) benzene, cyanated phenol dicyclopentadiene adduct , Cyanated novolak resin, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) ether, resorcin dicyanate, 2,2'-bis (4-cyanatophenyl) isopropylidene, 2,2 ' -Bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoroisopropylidene, 1,1,1-tris 4-cyanatophenyl) ethane, 2-phenyl-2- (4-cyanatophenyl) aromatic cyanate compounds such as isopropylidene are preferably exemplified.
The cyanate resin may be produced by a known method, or a commercially available product may be used. As a commercial item, the aromatic cyanate compound by a Huntsman company is mentioned suitably, for example.

The maleimide resin used in the composition of the present invention is not particularly limited, and a known maleimide resin can be used. Specifically, aromatic bismaleimide is preferably exemplified.
The aromatic bismaleimide can be obtained by a known method in which a corresponding aromatic diamine and maleic anhydride are reacted. Specific examples of the aromatic bismaleimide include N, N′-m-phenylene bismaleimide, N, N′-p-phenylene bismaleimide, N, N′-m-toluylene bismaleimide, N , N′-4,4′-biphenylenebismaleimide, N, N′-4,4 ′-(3,3′-dimethylbiphenylene) bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl And propane and bismaleimide represented by the following formula (7).

In the above formula (7), X represents —CH ₂ —, —C (CH ₃ ) ₂ —, —SO ₂ —, —SO— or —O—.

Specific examples of the bismaleimide represented by the above formula (7) include N, N′-4,4 ′-(3,3′-dimethyldiphenylmethane) bismaleimide, N, N′-4, 4 '-(3,3'-diethyldiphenylmethane) bismaleimide, N, N'-4,4'-diphenylmethane bismaleimide, N, N'-4,4'-2,2-diphenylpropane bismaleimide, N, N'-4,4'-diphenyl ether bismaleimide, N, N'-3,3'-diphenylsulfone bismaleimide, N, N'-4,4'-diphenylsulfone bismaleimide, N, N'-4,4 '-Diphenylsulfoxide bismaleimide, N, N'-4,4'-diphenyl sulfide bismaleimide, N, N'-4,4'-benzophenone bismaleimide and the like can be mentioned.
Among them, N, N′-4,4′-diphenylmethane bismaleimide (BDM), N, N′-4,4′-diphenyl ether bismaleimide, N, N′-m-toluylene bismaleimide, 2,2-bis A cured product of the composition from which [4- (4-maleimidophenoxy) phenyl] propane, N, N′-4,4′-diphenylsulfone bismaleimide, N, N′-4,4′-benzophenone bismaleimide is obtained. It is preferable from the point which is excellent in heat resistance. In particular, N, N′-4,4′-diphenylmethane bismaleimide, N, N′-4,4′-diphenyl ether bismaleimide, N, N′-m-toluylene bismaleimide, 2,2-bis [4- (4-Maleimidophenoxy) phenyl] propane is more preferred.
The above-mentioned aromatic bismaleimides may be used alone or in combination of two or more.

  It is preferable that the composition of the present invention further contains a curing agent. As the curing agent, a commonly used curing agent can be used without particular limitation, depending on the type of thermosetting resin to be used. Specifically, for example, amine compounds, acid anhydride compounds, amide compounds, phenol compounds, thiol compounds, imidazoles, boron trifluoride-amine complexes, guanidine derivatives, and the like can be used. Of these compounds, preferred are acid compounds, acid anhydride compounds, imidazole, dicyandiamide and the like.

  Specific examples of amine compounds include metaxylylenediamine (MXDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), norbornanediamine (NBDA), diaminodiphenylmethane, diethylenetriamine, and triethylene. Amine compounds such as tetramine, tetraethylenepentamine, diaminodiphenylsulfone, isophoronediamine (IPDA), dicyandiamide, dimethylbenzylamine, ketimine compounds, polyamines of polyamide skeleton synthesized from dimer of linolenic acid and ethylenediamine, the following formula The compound etc. which are represented by (8) are mentioned. Among these, metaxylylenediamine (MXDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), norbornanediamine (NBDA), diaminodiphenylsulfone, and the like are good in workability and high in curability. preferable. In addition, the compounds represented by the following formulas (8) and (9) and various modified forms of diaminodiphenylsulfone are suitable because they have an aromatic nucleus in the skeleton, have high heat resistance, and have a long pot life. For example, it is suitably used for prepreg applications.

  Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl And hexahydrophthalic anhydride. Among these, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like are preferable because they are liquid at room temperature, have good workability, and have high curability.

  Specific examples of phenolic compounds include polycondensates of bisphenols, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes, phenols, and the like. Examples thereof include polymers with various diene compounds, polycondensates of phenols and aromatic dimethylol, or condensates of bismethoxymethylbiphenyl with naphthols or phenols, biphenols and modified products thereof.

  Specific examples of the thiol-based curing agent include butanedithiols, dithiols having 5 to 10 carbon atoms, aromatic thiols, and thiol compounds such as polythiol such as EpiCure QX40 (manufactured by Japan Epoxy Resin). It is done.

  Specific examples of aminobenzoic acid esters include trimethylene glycol-p-aminobenzoate, neopentyl glycol-p-aminobenzoate, and the like.

  0.6-1.2 equivalent is preferable with respect to the sum total of the epoxy group, cyanate group, and maleimide group in a composition, and, as for the usage-amount of a hardening | curing agent, 0.7-1.0 equivalent is more preferable.

The composition of the present invention preferably further contains a curing catalyst.
As the curing catalyst, a commonly used curing catalyst can be used without particular limitation, depending on the type of thermosetting resin to be used. Specifically, for example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) ) Phenol, tertiary amines such as 1,8-diaza-bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, metal compounds such as tin octylate, quaternary phosphonium salts, Examples thereof include 3-boron fluoride-amine complex and 3-boron chloride-amine complex. Of these, 3-boron fluoride-amine complex is preferred because of its strong catalytic action.

  0.05-10 mass parts is preferable with respect to 100 mass parts of the said thermosetting resins, and, as for content of a curing catalyst, 0.1-0.5 mass part is more preferable.

The composition of the present invention is, as necessary, a filler, a reaction retardant, an anti-aging agent, an antioxidant, a pigment (dye), a plasticizer, and a thixotropic agent, as long as the object of the present invention is not impaired. , Ultraviolet absorbers, flame retardants, solvents, surfactants (including leveling agents), dispersants, dehydrating agents, adhesion-imparting agents, antistatic agents, and other various additives.
Also, rubber components such as nitrile rubber and carboxy-modified nitrile rubber, polyethersulfone (PES), polyetheretherketone (PEEK), polyetherimide (PEI), polysulfone (PSF) and other thermoplastics such as polyphenylene sulfide and nylon A resin may be added.

  Examples of the filler include organic or inorganic fillers having various shapes. Specifically, for example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; calcium carbonate, magnesium carbonate, zinc carbonate; Waxite clay, kaolin clay, calcined clay; carbon black; these fatty acid treated products, resin acid treated products, urethane compound treated products, and fatty acid ester treated products. The content of the filler is preferably 10% by mass or less based on the physical properties of the cured product.

  Specific examples of the reaction retarder include alcohol-based compounds.

Specific examples of the anti-aging agent include hindered phenol compounds.
Specific examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).

  Specific examples of the pigment include organic pigments such as titanium oxide, zinc oxide, ultramarine blue, bengara, and carbon black.

  Specific examples of the plasticizer include, for example, dioctyl phthalate (DOP), dibutyl phthalate (DBP); dioctyl adipate, isodecyl succinate; diethylene glycol dibenzoate, pentaerythritol ester; butyl oleate, methyl acetylricinoleate; phosphorus Examples include tricresyl acid, trioctyl phosphate; propylene glycol polyester adipate, butylene glycol polyester adipate, and the like. These may be used alone or in combination of two or more. From the viewpoint of workability, the content of the plasticizer is preferably 30 parts by mass or less with respect to 100 parts by mass of the thermosetting resin.

Specific examples of the thixotropic agent include aerosil (manufactured by Nippon Aerosil Co., Ltd.), disparon (manufactured by Enomoto Kasei Co., Ltd.), and the like.
Specific examples of the adhesion-imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and the like.

Specific examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether, and the like.
Examples of the antistatic agent generally include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

  The production method of the composition of the present invention is not particularly limited. For example, a method in which each of the above essential components and optional components are put in a reaction vessel and sufficiently kneaded using a stirrer such as a mixing mixer under reduced pressure. Can be used.

As a preferable example of the method for producing the composition of the present invention, at least one thermosetting resin selected from the group consisting of an epoxy resin, a cyanate resin and a bismaleimide resin, and a simple substance represented by the above formula (3) are used. A monomer, a monomer represented by the above formula (4) and a monomer represented by the above formula (5), and a polymerization initiator are mixed, and the above formula (3) is mixed in the thermosetting resin. ), A monomer represented by the above formula (4) and a monomer represented by the above formula (5), and a compound represented by the above formula (1) And a method for producing the composition of the present invention.
Another preferred example of the method for producing the composition of the present invention is at least one thermosetting resin selected from the group consisting of epoxy resins, cyanate resins, and bismaleimide resins, and the above formula (3). A monomer represented by the formula (4), a monomer represented by the formula (6), and a polymerization initiator, and in the thermosetting resin, The monomer represented by the above formula (3), the monomer represented by the above formula (4), and the monomer represented by the above formula (6) are copolymerized, and the above formula (2) And a method for producing the composition of the present invention by producing the represented compound.
In these production methods, the monomer has a relatively low viscosity as compared with the method in which the compound represented by the formula (1) or (2) is produced and then the compound is mixed with the thermosetting resin. Since it is easy to disperse | distribute in a thermosetting resin and the viscosity of the composition obtained becomes low, it is excellent in workability | operativity. Furthermore, according to this manufacturing method, it is possible to reduce VOCs and work processes.

The composition of the present invention described above can provide a cured product that is excellent in bending strength and bending elastic modulus and particularly excellent in toughness.
Therefore, the composition of the present invention can be used for a wide range of applications by taking advantage of the properties of the composition of the present invention. Specific examples include adhesives, paints, electric / electronic materials, aircraft structural materials, and the like. In particular, it is suitably used as a matrix resin for a prepreg of an aircraft structural material.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Synthesis of vinylbenzyl-ω-methyl-polyoxyethylene oxide>
After adding 60 g of polyethylene glycol monomethyl ether (Mn = 2000) to 300 ml of THF, 0.09 mol of a small excess of sodium hydride was added under a nitrogen atmosphere at room temperature. After the generation of hydrogen was stopped, 22.9 g of chloromethylstyrene was added and reacted at 60 ° C. for 15 hours to obtain vinylbenzyl-ω-methyl-polyoxyethylene oxide represented by the following formula (10). This was used in the following synthesis examples and examples.

  In the above formula (10), q represents 45.

<Synthesis of the compound of the present invention>
(Synthesis Example 1)
In 600 ml of acetone, 0.07 mol of styrene, 0.1 mol of N-phenylmaleimide and 0.03 mol of vinylbenzyl-ω-methyl-polyoxyethylene oxide, and AIBN (manufactured by Kanto Chemical Co., Inc.) monomer as an initiator 0.01 mol% was added and stirred at 80 ° C. for 8 hours. Next, the obtained solution was reprecipitated with THF-methanol to obtain a white polymer represented by the following formula (11).
The obtained compound was dissolved in CDCl ₃ , and the structure was confirmed by ¹ H-NMR using tetramethylsilane (TMS) as a standard substance. A ¹ H-NMR spectrum of the compound of Synthesis Example 1 is shown in FIG.
^From the result of ¹ H-NMR, it was found that the introduction rate of the polyether chain was 15 mol%. Here, the introduction rate of the polyether chain is the molar fraction of the polyether portion determined from the hydrogen ratio in the polymer.
The obtained compound had a weight average molecular weight of 300,000, a molecular weight distribution (M _w / M _n ) of 3.2, and a glass transition point of 188 ° C. In addition, the weight average molecular weight in this specification is a standard polystyrene conversion value by a gel permeation chromatography method.

The ratio (a / b) between a and b in the above formula, determined from the ratio of aromatic hydrogen to methylene hydrogen in the polyether part by ¹ H-NMR spectrum, was 85/15.
Moreover, q was 45.

(Synthesis Example 2)
Instead of vinylbenzyl-ω-methyl-polyoxyethylene oxide, 0.03 mol of ω-methyl-polyoxyethylene glycol methacrylate (manufactured by Aldrich, the same shall apply hereinafter) was used, except for reaction at 80 ° C. for 9 hours. Obtained a white polymer represented by the following formula (12) in the same manner as in Synthesis Example 1.
The obtained compound was dissolved in CDCl ₃ , and the structure was confirmed by ¹ H-NMR using tetramethylsilane (TMS) as a standard substance. The ¹ H-NMR spectrum of the compound of Synthesis Example 2 is shown in FIG.
^From the result of ¹ H-NMR, it was found that the introduction rate of the polyether chain was 15 mol%.
Moreover, the number average molecular weight of the obtained compound was 350,000, molecular weight distribution ( _Mw / _Mn ) was 3.0, and the glass transition point ( _Tg ) was 190 degreeC.

The ratio (c / d) between c and d in the above formula, determined from the ratio of aromatic hydrogen to methylene hydrogen in the polyether part by ¹ H-NMR spectrum, was 85/15.
R was 45.

<Examples 1-8 and Comparative Examples 1-5>
Each component of the following Table 1 was mixed with the composition (parts by mass) shown in Table 1 using a stirrer to obtain each composition shown in Table 1.
Using each of the obtained compositions, bending strength, bending elastic modulus and toughness were evaluated by the following methods.
The results are shown in Table 1.

(Bending strength and flexural modulus)
According to JIS K7171, each obtained composition was cured at 85 ° C. for 5 hours, further cured at 150 ° C. for 15 hours to prepare a test piece, and bending strength and bending elastic modulus were measured.

(Toughness)
Each composition obtained was heated from room temperature to 180 ° C. at 2 ° C./min and then cured at 180 ° C. for 2 hours to obtain a test specimen. Using this specimen, the fracture toughness value (K _IC ) was measured according to ASTM E399.

The components shown in Table 1 are as follows.
・ Epoxy resin (bisphenol A type epoxy resin): YD-128, manufactured by Tohto Kasei Co., Ltd., the same shall apply hereinafter. Hydrophthalic anhydride): MH-700, manufactured by Shin Nippon Rika Co., Ltd.

PMS (compound represented by the following formula (13)): 0.1 mol of styrene (manufactured by Kanto Chemical Co., Inc.) and 0.1 mol of N-phenylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) in acetone / toluene = 1/1 It melt | dissolved in 600 ml of solvent, 0.33g of AIBN (made by Kanto Chemical Co., Inc.) was added, and it was made to react at 65 degreeC under nitrogen stream for 8 hours. Then, reprecipitation was performed with THF-methanol to obtain an N-phenylmaleimide-styrene alternating copolymer (PMS) represented by the following formula (13). In formula (13), s is an integer of 550 to 600.
The compound (PMS) obtained had a yield of 96%, a weight average molecular weight (M _w ) of 397,000, a molecular weight distribution (M _w / M _n ) of 2.4, and a glass transition temperature (T _g ) of 228 ° C. .

As is apparent from the results shown in Table 1 above, a composition containing the compound represented by formula (13) instead of the compound of Synthesis Example 1 or Synthesis Example 2 (Comparative Example 2), and Synthesis Example 1 The composition containing 40 parts by mass of the compound (Comparative Example 3) had improved toughness as compared with Comparative Example 1, but had lower toughness than Examples 1-8. Further, Comparative Example 2 and Comparative Example 3 had lower bending strength than Comparative Example 1. Moreover, although the comparative example 5 had improved toughness compared with the comparative example 4, it was lower toughness than Examples 1-8. Further, Comparative Example 5 had lower bending strength than Comparative Example 4.
On the other hand, in Examples 1 to 8, the fracture toughness value is 2.3 to 2.6 times that of the composition containing only the epoxy resin and 4,4′-DDS (Comparative Example 1), which is markedly tougher. Was excellent. Furthermore, there was almost no decrease in bending strength and bending elastic modulus.

<Example 9>
Into the bisphenol A type epoxy resin, 0.07 mol of styrene, 0.1 mol of N-phenylmaleimide and 0.03 mol of vinylbenzyl-ω-methyl-polyoxyethylene oxide are added so that the total mass becomes 10 wt%. And dissolved at 50 ° C. Next, 0.01 mol% of benzoyl peroxide (BPO) as a polymerization initiator with respect to all monomers, MHHPA as a curing agent in an equivalent amount to the epoxy group in the mixture, and 0.1 g of benzyldimethylamine as a catalyst were added. And fully dispersed.
The mixture was poured into a mold, cured at 85 ° C. for 5 hours, then cured at 100 ° C. for 5 hours, and further cured at 150 ° C. for 15 hours to be cured.
Using the obtained cured product, the bending strength, the flexural modulus and the fracture toughness value were measured in the same manner as in the above method.
The results are shown in Table 2 below.

<Example 10>
Into the bisphenol A type epoxy resin, 0.09 mol of styrene, 0.1 mol of N-phenylmaleimide and 0.01 mol of ω-methyl-polyoxyethylene glycol methacrylate were added so that the total mass was 10 wt%. It was dissolved at ° C. Next, AIBN as a polymerization initiator is 0.01 mol% with respect to all monomers, MHHPA as a curing agent is equivalent to an epoxy group in the mixture, and 0.1 g of benzyldimethylamine is added as a catalyst and sufficiently dispersed. It was.
The mixture was poured into a mold, cured at 85 ° C. for 5 hours, then cured at 100 ° C. for 5 hours, and further cured at 150 ° C. for 15 hours.
Using the obtained cured product, the bending strength, the flexural modulus and the fracture toughness value were measured in the same manner as in the above method.
The results are shown in Table 2 below.

  As is apparent from the results shown in Table 2, Example 9 and Example 10 were excellent in toughness with almost no decrease in bending strength and bending elastic modulus, as in Examples 1-8.

1 is a ¹ H-NMR spectrum of the compound of Synthesis Example 1. FIG. FIG. 2 is a ¹ H-NMR spectrum of the compound of Synthesis Example 2.

Claims (5)

A compound represented by the following formula (1) or (2).

(In the formula, R ¹ is any ^one of a phenyl group, a substituted phenyl group, a cyclohexyl group, and an alkyl group having 1 to 6 carbon atoms;
R ² is — (CH ₂ CH ₂ O) _p R ⁴ , p is an integer of 1 to 150, R ⁴ is a phenyl group, a substituted phenyl group, a cyclohexyl group, and a carbon number of 1 to 6. Any of the alkyl groups of
R ³ is a hydrogen atom or a methyl group,
The ratio of n to m (n / m) is 1000/1 to 80/20. )   The compound according to claim 1, having a weight average molecular weight of 5,000 to 700,000. At least one thermosetting resin selected from the group consisting of epoxy resins, cyanate resins and bismaleimide resins;
The compound represented by the formula (1) and / or the compound represented by the formula (2) according to claim 1 or 2,
The thermosetting resin whose content of the compound represented by said Formula (1) and / or the compound represented by said Formula (2) is 1-30 mass parts with respect to 100 mass parts of said thermosetting resins. Composition. At least one thermosetting resin selected from the group consisting of epoxy resins, cyanate resins and bismaleimide resins, a monomer represented by the following formula (3), and a single monomer represented by the following formula (4) And a monomer represented by the following formula (5) and a polymerization initiator are mixed,
In the thermosetting resin, a monomer represented by the following formula (3), a monomer represented by the following formula (4), and a monomer represented by the following formula (5) are copolymerized. The thermosetting resin composition according to claim 3, which is obtained by generating a compound represented by the formula (1).

(In the formula, R ¹ is any ^one of a phenyl group, a substituted phenyl group, a cyclohexyl group, and an alkyl group having 1 to 6 carbon atoms;
R ² is — (CH ₂ CH ₂ O) _p R ⁴ , p is an integer of 1 to 150, R ⁴ is a phenyl group, a substituted phenyl group, a cyclohexyl group, and a carbon number of 1 to 6. Any one of the alkyl groups. ) At least one thermosetting resin selected from the group consisting of epoxy resins, cyanate resins and bismaleimide resins, a monomer represented by the following formula (3), and a single monomer represented by the following formula (4) And a monomer represented by the following formula (6) and a polymerization initiator are mixed:
In the thermosetting resin, a monomer represented by the following formula (3), a monomer represented by the following formula (4), and a monomer represented by the following formula (6) are copolymerized. The thermosetting resin composition according to claim 3, which is obtained by generating a compound represented by the formula (2).

(In the formula, R ¹ is any ^one of a phenyl group, a substituted phenyl group, a cyclohexyl group, and an alkyl group having 1 to 6 carbon atoms;
R ² is — (CH ₂ CH ₂ O) _p R ⁴ , p is an integer of 1 to 150, R ⁴ is a phenyl group, a substituted phenyl group, a cyclohexyl group, and a carbon number of 1 to 6. Any of the alkyl groups of
R ³ is a hydrogen atom or a methyl group. )

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