JP5424021B2 - Resin composition for fiber reinforced composite material, cured product thereof, resin composition for printed wiring board, fiber reinforced composite material, fiber reinforced resin molded product, and production method thereof - Google Patents

Description

  The present invention is a fiber-reinforced composite material suitable for aircraft members, spacecraft members, automobile members, etc., because it exhibits excellent fluidity and is excellent in heat resistance and mechanical strength in its cured product, its production method, and The present invention relates to a matrix resin material of a fiber reinforced composite material.

  An epoxy resin composition containing an epoxy resin and its curing agent as essential components is excellent in various physical properties such as high heat resistance, moisture resistance, and dimensional stability. Electronic parts such as conductive paste, conductive adhesives such as conductive paste and other adhesives, liquid sealing materials such as underfill, liquid crystal sealing materials, flexible substrate coverlays, build-up adhesive films, paints, photoresist materials, Widely used in color materials, fiber reinforced composite materials, etc.

  Among these, fiber reinforced composite materials made by impregnating and curing reinforcing fibers as matrix components with an epoxy resin and a curing agent are particularly high heat resistance and low cure shrinkage in addition to their characteristics of light weight and high strength. In view of having various performances such as chemical resistance and high elastic modulus, there is a high demand in general industrial fields such as the automobile industry and aerospace industry.

  However, since epoxy resins are generally highly viscous fluids or solids at room temperature, it is necessary to heat the resin component in order to ensure a practical level of fluidity of the epoxy resin in the step of impregnating the fiber reinforcement with resin. However, the curing of the epoxy resin is accelerated by heating, and on the contrary, there has been a problem that the viscosity is increased and the impregnation is poor. In particular, in the field of carbon fiber reinforced thermosetting plastics (CFRP), the resin transfer molding (RTM) method, which has been spreading in recent years due to overwhelming cycle time and low equipment cost, Low viscosity and high fluidity were essential characteristics.

  Therefore, as an epoxy resin material suitable for the RTM method in CFRP applications, for example, an epoxy equivalent of 200 g / eq. The following bisphenol F type epoxy resin is used as the main agent, and the fluidity of the thermosetting resin component is improved by using an aromatic polyamine that is liquid at room temperature and a Lewis acid / base complex as the curing agent component. In addition, a technique for further improving low temperature curability and improving CFRP productivity in the RTM method is known (see Patent Document 1).

  However, the epoxy equivalent of 200 g / eq. The thermosetting resin material containing the following bisphenol F type epoxy resin, aromatic polyamine liquid at room temperature, and Lewis acid and base complex is intended to reduce the viscosity of the epoxy resin itself, but the entire composition However, the viscosity is still high and it is difficult to sufficiently improve the molding cycle of the RTM molding, and further, the heat resistance in the cured product is not sufficient and it is difficult to apply to the automobile industry and the aerospace industry.

  On the other hand, in the field of printed wiring boards, solvent-based varnishes have been actively developed in response to environmental loads such as VOC problems in recent years. For example, liquid epoxy resins represented by low molecular weight bisphenol type epoxy resins, acid anhydrides, and the like Non-solvent varnishes blended with epoxy resin curing agents represented by the above are widely used. However, a cured product obtained by curing such a low molecular weight bisphenol type epoxy resin with a curing agent for epoxy resin does not have a sufficient heat resistance itself, and heat when using lead-free solder or mounting a high-frequency type semiconductor device. There was a problem of insufficient resistance to history. In addition, as a varnish for printed wiring boards with excellent heat resistance of cured products, a vinyl ester resin obtained by reacting a novolac type epoxy resin or a bisphenol type epoxy resin with methacrylic acid is mixed with an unsaturated monomer and varnished. Technology is also known (Patent Document 2 below). However, when a vinyl ester resin obtained by reacting a novolak epoxy resin with methacrylic acid is used, its varnish viscosity is remarkably high, impairing the impregnation of the glass cloth, and the printed wiring board productivity is low. It was. On the other hand, when a vinyl ester resin obtained by reacting a liquid bisphenol-type epoxy resin with methacrylic acid is used, the varnish viscosity is low, but the heat resistance is not sufficient.

JP 2006-265434 A Japanese Patent No. 3415610

  Accordingly, the problem to be solved by the present invention is a curable resin composition that has excellent fluidity and gives excellent heat resistance to a cured product, and the cured product, a resin for printed wiring boards having high heat resistance and high fluidity. An object of the present invention is to provide a composition, a fiber-reinforced composite material that imparts excellent heat resistance to a molded article, a fiber-reinforced resin molded article that is excellent in heat resistance, and a method for producing a fiber-reinforced resin molded article that has good productivity.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyfunctional epoxy resin (A) containing a naphthalene skeleton in the molecular structure, an acid group-containing radically polymerizable monomer having a molecular weight of 300 or less ( B) and radical polymerization initiator (C) are used in combination, and these are cured continuously or simultaneously, so that curing by a so-called in-situ polymerization reaction is performed, that is, the acid groups in the monomer (B) are By reacting with the epoxy group in the polyfunctional epoxy resin (A) and polymerizing the radically polymerizable group resulting from the monomer (B), it is in a low temperature range of 50 ° C. or lower before curing. However, it has been found that excellent fluidity is exhibited and, at the same time, excellent heat resistance is exhibited after curing, and the present invention has been completed.

  That is, the present invention provides a polyfunctional epoxy resin (A) containing a naphthalene skeleton in the molecular structure, an acid group-containing radical polymerizable monomer (B) having a molecular weight of 300 or less, and a radical polymerization initiator (C). The present invention relates to a curable resin composition as an essential component.

  The present invention further relates to a cured product obtained by in situ reaction of the resin composition for fiber-reinforced composite material.

  The present invention further provides a fiber reinforced composite comprising injecting and impregnating the resin composition for fiber reinforced composite material into a base material composed of reinforced fibers arranged in a mold, followed by in-situ curing. The present invention relates to a material manufacturing method.

  According to the present invention, a curable resin composition excellent in fluidity and imparting excellent heat resistance to a cured product, the cured product, a resin composition for printed wiring boards having high heat resistance and high fluidity, and a molded product. It is possible to provide a fiber-reinforced composite material that gives excellent heat resistance, a fiber-reinforced resin molded product that is excellent in heat resistance, and a method for manufacturing a fiber-reinforced resin molded product that has good productivity.

Hereinafter, the present invention will be described in detail.
The liquid curable resin composition of the present invention includes, as its thermosetting resin component, a polyfunctional epoxy resin (A) containing a naphthalene skeleton in the molecular structure, an acid group-containing radical polymerizable monomer having a molecular weight of 300 or less. (B) and radical polymerization initiator (C) are essential components. Then, after impregnating these components into the fiber reinforcement, the reaction is performed continuously or simultaneously, that is, the reaction between the epoxy group and the acid group, and the polymerization reaction of the radical polymerizable group, in particular as reaction steps. It is characterized by performing both reactions simultaneously or continuously without distinction. By curing by in-situ polymerization reaction in this way, the fluidity is remarkably increased before curing, while the heat resistance of the cured product can be dramatically improved. If this point is further spread, the cured product obtained by the in-situ reaction in the present invention comprises the polyfunctional epoxy resin (A) and an acid group-containing radical polymerizable monomer (B) having a molecular weight of 300 or less. After pre-reaction and vinyl esterification, the heat resistance can be further enhanced compared to radical polymerization of this, and as a result, it exhibits excellent fluidity before curing and after curing. Exhibits an unprecedented heat resistance.

  The polyfunctional epoxy resin (A) used in the present invention is characterized by containing a naphthalene skeleton in the molecular structure, and thereby has excellent heat resistance in a cured product. In addition, the polyfunctional epoxy resin (A) preferably has a softening point of 100 ° C. or lower from the viewpoint of better fluidity at low temperatures. Here, the softening point is the softening point of the ring and ball method (B & R method) based on “JIS-K2531”, and the softening point of 100 ° C. or lower includes a semi-solid epoxy resin.

  Specifically, this polyfunctional epoxy resin (A) is represented by the following structural formula 1

（式中、Ｒ^１及びＲ^２は、それぞれ独立的に水素原子、メチル基、又はエチル基を表し、Ｒ^３は、それぞれ独立的に、水素原子又メチル基を表し、ｎは繰り返し単位数を表す。）で表され、かつ、該構造式１中のｎ＝０体の含有率が８０〜９８質量％である半固形状のジグリシジルオキシナフタレン型エポキシ樹脂（Ａ１）、又は、下記構造式２

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a methyl group, or an ethyl group, R ³ each independently represents a hydrogen atom or a methyl group, and n represents the number of repeating units. And a semi-solid diglycidyloxynaphthalene type epoxy resin (A1) in which the content of n = 0 in the structural formula 1 is 80 to 98% by mass, or the following structural formula 2

（式中、Ｒ^３及びＲ^４は、それぞれ独立して水素原子、炭素原子数１〜４の炭化水素基、又は炭素原子数１〜４のアルコキシ基を示す。）
で表される多官能型エポキシ樹脂（Ａ２）、その他ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ビフェニル変性ナフトール型エポキシ樹脂（ビスメチレン基でナフトール核が連結された多価ナフトール樹脂のエポキシ化合物）等が挙げられる。

(In the formula, R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.)
Naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, naphthol aralkyl type epoxy resin, biphenyl-modified naphthol type epoxy resin (with bismethylene group) And an epoxy compound of a polyvalent naphthol resin linked with a naphthol nucleus).

The diglycidyloxynaphthalene type epoxy resin (A1) used here is
As described above, the following structural formula 1

（式中、Ｒ^１及びＲ^２は、それぞれ独立的に水素原子、メチル基、又はエチル基を表し、Ｒ^３は、それぞれ独立的に、水素原子又メチル基を表し、ｎは繰り返し単位数を表す。）で表され、かつ、該構造式１中のｎ＝０体の含有率が８０〜９８質量％である

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, a methyl group, or an ethyl group, R ³ each independently represents a hydrogen atom or a methyl group, and n represents the number of repeating units. And the content of n = 0 isomer in the structural formula 1 is 80 to 98% by mass.

The content of n = 0 isomers in the structural formula 1 can be determined by GPC measurement. Specifically, the following conditions can be adopted as GPC measurement conditions.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

  The epoxy resin (A1) is obtained by reacting dihydroxynaphthalene and epihalohydrin.

  Specific examples of the dihydroxynaphthalene used here include 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and Examples thereof include compounds in which these methyl groups or ethyl groups are substituted by a nucleus. Among these, 1,6-dihydroxynaphthalene is preferable from the viewpoint of low viscosity and excellent fluidity.

  On the other hand, specific examples of the epihalohydrin to be reacted therewith include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Among these, epichlorohydrin is particularly preferable from the viewpoint of fluidity and reactivity of the epoxy resin (A).

  The epoxy resin (A1) thus obtained has an epoxy equivalent of 136 to an epoxy equivalent, because when the epoxy equivalent becomes large, the distance between the crosslinking points in the cured product becomes long and the crosslinking density tends to decrease. 160 g / eq. It is preferable that it is the range of these.

  On the other hand, the trifunctional epoxy resin (A2) has the following structural formula 2 as described above.

（式中、Ｒ^３及びＲ^４は、それぞれ独立して水素原子、炭素原子数１〜４の炭化水素基、又は炭素原子数１〜４のアルコキシ基を示す。）
で表されるものである。
この構造式２で表される多官能型エポキシ樹脂（Ａ２）は、具体的には、下記構造式２−１〜構造式２−８で表されるものが挙げられる。

(In the formula, R ³ and R ⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.)
It is represented by
Specific examples of the polyfunctional epoxy resin (A2) represented by Structural Formula 2 include those represented by Structural Formula 2-1 to Structural Formula 2-8 below.

  In the present invention, among the polyfunctional epoxy resins (A2), the epoxy resin represented by the structural formula 2-1 is particularly preferable from the viewpoint that the heat resistance of the cured product is increased.

The polyfunctional epoxy resin (A2) can be produced by a method in which 2,7-dihydroxynaphthalene and formaldehyde are reacted in the presence of an alkali catalyst, and then the resulting reaction product is reacted with an epihalohydrin. In this case,
In addition to the compound represented by the structural formula 2 (hereinafter abbreviated as “compound (a)”),
Structural formula (i)

で表される化合物（ｂ）や、或いは、前記化合物（ａ）における芳香核に更に、下記部分構造式（ii）

Or the aromatic nucleus in the compound (a), and the following partial structural formula (ii):

で表される構造部位が結合したエポキシ樹脂オリゴマー（ｃ）、更に、
前記方法において、エピハロヒドリンを反応させる際に生成するオリゴマー（ｄ）も生成するため、前記多官能型エポキシ樹脂（Ａ２）は、これらの混合物として使用してもよい。

An epoxy resin oligomer (c) to which a structural moiety represented by
In the said method, since the oligomer (d) produced | generated when making an epihalohydrin react is also produced | generated, you may use the said polyfunctional type epoxy resin (A2) as these mixtures.

  Thus, when using the said polyfunctional epoxy resin (A2) as a mixture, it is preferable to contain the said compound (a) in the ratio used as 5.0-20.0 mass%, specifically, the said compound (A) is 5.0 to 20.0% by mass, the compound (b) is 15.0 to 50.0% by mass, and other oligomer components represented by the oligomer (c) or oligomer (d) are 30 to 30%. It is preferable to contain it in the ratio which will be 80 mass% from the point which is excellent in the solubility to monomer components, such as an acid group containing radically polymerizable monomer (B) and a radically polymerizable monomer (D).

  The polyfunctional epoxy resin (A2) preferably has an epoxy equivalent in the range of 150 to 300 g / eq from the viewpoint of good heat resistance and low coefficient of thermal expansion, and particularly 155 to 250 g / eq. It is preferable that it is the range of these.

  As described above, the polyfunctional epoxy resin (A2) can be produced by the above-described method. However, the present invention is characterized in that the amount of alkali catalyst is larger than that in the prior art. The alkali catalyst is used in a proportion of 0.2 to 2.0 times the molar amount with respect to 7-dihydroxynaphthalene or the total number of moles of 2,7-dihydroxynaphthalene and phenol. Thus, a skeleton in which a naphthalene structure and a cyclohexadienone structure are knotted via a methylene group can be generated in the molecular structure.

  Here, 2,7-dihydroxynaphthalene used in the above method is 2,7-dihydroxynaphthalene, methyl-2,7-dihydroxynaphthalene, ethyl-2,7-dihydroxynaphthalene, t-butyl-2,7-dihydroxy. Naphthalene, methoxy-2,7-dihydroxynaphthalene, ethoxy-2,7-dihydroxynaphthalene and the like can be mentioned.

  The formaldehyde used in the above method may be a formalin solution in an aqueous solution or paraformaldehyde in a solid state.

Examples of the alkali catalyst used in the above method include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, inorganic alkalis such as metal sodium, metal lithium, sodium hydride, sodium carbonate and potassium carbonate. It is done.

  Subsequently, the target epoxy resin (A2) is obtained by making the obtained phenolic compound and epihalohydrin react. Specifically, for example, epihalohydrin is added in a ratio of 2 to 10 times the amount (molar basis) with respect to the number of moles of the phenolic hydroxyl group in the phenolic compound, and further 0.9% relative to the number of moles of the phenolic hydroxyl group. A method of reacting at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while adding or gradually adding up to 2.0 times (molar basis) of the basic catalyst is mentioned. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. Alternatively, the solution may be separated and further separated to remove water and the epihalohydrin is continuously returned to the reaction mixture.

Next, the acid group-containing radical polymerizable monomer (B) having a molecular weight of 300 or less used in the present invention reacts with the epoxy resin (A) and at the same time, causes polymerization of an acryloyl group by radical polymerization. In this invention, the heat resistance of hardened | cured material can be improved greatly by making it harden | cure by such an in-situ reaction. Specifically, the acid group-containing radically polymerizable monomer (B) includes acrylic acid, methacrylic acid, maleic acid, methacrylic anhydride; hydroxyl group-containing (meta) such as hydroxyethyl methacrylate, hydroxybutyl methacrylate, and hydroxypropyl methacrylate. ) Acrylate, aliphatic acid anhydrides such as succinic anhydride and maleic anhydride, aliphatic carboxylic acids such as adipic acid; or aromatic carboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc. And the reaction product.

  Among these, from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and acid anhydrides thereof, in particular, from the point of excellent viscosity reduction effect and heat resistance of the cured product. Acrylic acid and methacrylic acid are particularly preferable, and methacrylic acid is particularly preferable from the viewpoint of the effect of reducing the viscosity and excellent heat resistance of the cured product.

  The compounding ratio of the epoxy resin (A) detailed above and the acid group-containing radical polymerizable monomer (B) having a molecular weight of 300 or less is the epoxy resin (A) and the acid group-containing radical polymerizable monomer having a molecular weight of 300 or less. 40 to 90 parts by mass of the epoxy resin (A) and 10 to 60 parts by mass of the acid group-containing radical polymerizable monomer (B) having a molecular weight of 300 or less with respect to 100 parts by mass of the total of (B). A ratio is preferable from the viewpoint that a good balance between the fluidity of the composition and the heat resistance of the cured product is obtained.

  The liquid curable resin composition of the present invention is used in combination with another epoxy resin of a polyfunctional epoxy resin (A) containing a naphthalene skeleton in the molecular structure as an epoxy resin component as long as the fluidity of the composition is not impaired. May be.

  The other epoxy resin is not particularly limited, and various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type Bifunctional type such as epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, sulfur containing epoxy resin, stilbene type epoxy resin Epoxy resin, triglycidyl isosocyanurate, methoxynaphthalene-modified aralkyl epoxy resin, methoxynaphthalene-modified novolak resin, phenol novolac epoxy resin, cresol novo Type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin (commonly known as an epoxidized product of zylock resin), naphthol formaldehyde condensation type epoxy Resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolak Type epoxy resin (epoxidized polyhydric phenol resin in which phenol nucleus is linked by bismethylene group), biphenyl modified naphthol type epoxy resin ( (Epoxy compound of polyvalent naphthol resin in which naphthol core is linked by smethylene group), alkoxy group-containing novolak type epoxy resin, alkoxy group-containing phenol aralkyl resin, tetrabromobisphenol A type epoxy resin, brominated phenol novolak type epoxy resin, etc. Can be mentioned. Moreover, the said epoxy resin may be used independently and may mix 2 or more types. Among these epoxy resins, bisphenol F-type epoxy resins, biphenyl-type epoxy resins, and tetramethylbiphenyl-type epoxy resins are preferable in terms of particularly low viscosity, and phenol aralkyl-type epoxy resins and biphenyls are preferable in terms of excellent flame retardancy. A modified novolac type epoxy resin is preferred. The amount of these epoxy resins used is an epoxy equivalent of 500 g / eq. It is preferable that it is the range of 5-80 mass parts with respect to 100 mass parts of the following epoxy resins (A).

  The radical polymerization initiator (C) used in the present invention is not particularly limited as long as it is used as a thermal radical polymerization initiator. For example, methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1, 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5 -Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) ) Cyclododecane, n-butyl 4,4-bis (t-butyl pero) B) Valerate, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl hydroperoxide, P-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α '-Bis (t-butylperoxy) diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, Isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide Id, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutylperoxy Dicarbonate, di-2-ethylhexylperoxydicarbonate, di-sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxy Dicarbonate, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl- 1-methyl Ethyl peroxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl- 2,5-bis (2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethyl Hexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t- Butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylper Oxybenzoate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, t-butylperoxyallyl monocarbonate, 3,3 ′, 4,4 Examples include '-tetra (t-butylperoxycarbonyl) benzophenone. The radical polymerization initiator (C) is used in an amount of 0.001% by mass to 5% by mass with respect to the total mass of the radical polymerizable component and the total mass of the radical polymerization initiator (C). Preferably it is done.

  In the curable resin composition of the present invention, a reaction catalyst for reacting the bisphenol-type epoxy resin (A) with the acid group-containing radical polymerizable monomer (B) can be used in combination as appropriate. Examples of the reaction catalyst include tertiary amines such as triethylamine, N, N-benzyldimethylamine, N, N-dimethylphenylamine, N, N-dimethylaniline or diazabicyclooctane; trimethylbenzylammonium chloride, triethylbenzyl Quaternary ammonium salts such as ammonium chloride and methyltriethylammonium chloride; phosphines such as triphenylphosphine and tributylphosphine; imidazoles such as 2-methylimidazole, 1,2-dimethylimidazole and 2-ethyl-4-methylimidazole; Examples include triphenyl stibine and anion exchange resin. The catalyst is used in an amount of 0.01 to 0.5% by mass, particularly 0.05 to 5% by mass, in the resin composition for fiber-reinforced composite material, which is a varnish. To preferred.

  In the present invention, the normal epoxy resin is used in a proportion of less than 80%, preferably less than 50%, particularly preferably less than 30% of the epoxy group of the polyfunctional epoxy resin (A) bisphenol type epoxy resin (A). A curing reaction may be caused by the curing agent for use.

Examples of the epoxy resin curing agent that can be used here include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivatives; dicyandiamide Amide compounds such as polyamide resin synthesized from dimer of linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acid anhydride compounds such as methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin Polyhydric phenol compounds such as phenol resin, dicyclopentadiene phenol addition resin, triphenylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin; Examples thereof include benzaldehyde resins, naphthol benzaldehyde resins, phenol naphthaldehyde resins, naphthol naphthaldehyde resins, aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked by melamine, benzoguanamine, or the like). When using these epoxy resin curing agents, the active hydrogen in the curing agent is less than 0.8 equivalent, preferably 0.5, based on the epoxy groups of the bisphenol type epoxy resin (A). The range is less than equivalent, particularly preferably less than 0.3 equivalent.

  The liquid curable resin composition of the present invention has been described above in terms of being able to impart functionalities such as appropriate flexibility and strength to the cured product depending on the application, and further reducing the viscosity of the varnish. It is preferable to use another radical polymerizable monomer (D) in combination with the component (B). Examples of the radical polymerizable monomer that can be used here include styrene, methylstyrene, halogenated styrene, divinylbenzene, and (meth) acrylic acid esters represented by the following.

  Examples of the monofunctional (meth) acrylate that can be used in the present invention include methyl, ethyl, propyl, butyl, 3-methoxybutyl, amyl, isoamyl, 2-ethylhexyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, Tridecyl, hexadecyl, octadecyl, stearyl, isostearyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclo (Meth) acrylate etc. which have substituents, such as pentenyloxyethyl, are mentioned.

  Examples of the polyfunctional (meth) acrylate include 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. Di (meth) such as neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane dimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol Di (meth) acrylate of diol obtained by adding 2 mol or more of ethylene oxide or propylene oxide to 1 mol of 1,6-hexanediol, acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate , Di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, Diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A Di (meth) acrylate, 3 mol or more of ethylene oxide or propylene oxide added to 1 mol of trimethylolpropane, diol or tri (meth) acrylate of triol, 4 mol or more of ethylene oxide or propylene per 1 mol of bisphenol A Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra of diol obtained by adding oxide Meth) acrylate, dipentaerythritol poly (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, ethylene oxide-modified alkylated phosphoric acid (meth) acrylate.

  In addition to the above (meth) acrylates, functional oligomers containing ethylenic double bonds such as urethane (meth) acryl oligomers and epoxy (meth) acryl oligomers may be added as necessary. These can be used alone or in combination of two or more at any ratio.

  Here, the amount of the radical polymerizable monomer (D) used is the polyfunctional epoxy resin (A) containing a naphthalene skeleton in the molecular structure, the acid group-containing radical polymerizable monomer (B), and the radical. The acid group-containing radical polymerizable monomer (B) and the radical polymerizable monomer (D) with respect to 100 parts by mass of the total mass of the polymerization initiator (C) and the radical polymerizable monomer (D). It is preferable that it is a ratio from which the total mass becomes 5-50 mass%. In the range of 5% by weight or more, the impregnation property to the fiber base material is good, and in the range of 50% by weight or less, the dimensional stability and high heat resistance of the molded product which is a cured product are excellent.

  The liquid curable resin composition of the present invention described in detail above can further use a flame retardant from the viewpoint of imparting flame retardancy to the cured product. Examples of the flame retardant used here include halogen-based flame retardants such as polybrominated diphenyl ether, polybrominated biphenyl, tetrabromobisphenol A, and tetrabromobisphenol A type epoxy resin, and phosphorus-based flame retardants, nitrogen-based flame retardants, and silicones. Non-halogen flame retardants such as flame retardants, inorganic flame retardants, and organic metal salt flame retardants. Of these, non-halogen flame retardants are preferred because of the recent high demand for non-halogens.

  Various compounding agents, such as a silane coupling agent, a mold release agent, an ion trap agent, a pigment, can be added to the curable resin composition of this invention as needed.

  The curable resin composition of the present invention can be easily obtained as a liquid composition by uniformly stirring the above-described components.

  As described above, the curable resin composition of the present invention is a liquid composition at room temperature, and can be varnished without using an organic solvent or by using a very small amount. Here, acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, methanol, ethanol and the like can be mentioned. The amount of the organic solvent used is preferably 10% by mass or less in the composition, and it is particularly preferable that the organic solvent is not substantially used.

  The curable resin composition of this invention can be manufactured by mixing each above-mentioned component uniformly. The liquid curable resin composition thus obtained, that is, the varnish for impregnating reinforcing fibers, is liquid at room temperature (25 ° C.), has excellent fluidity, and exhibits extremely high heat resistance after curing. It will have the characteristics. Specifically, the varnish obtained by uniformly mixing the above-mentioned components has a viscosity measured at 25 ° C. using an E-type viscometer (“TV-20 type” cone plate type manufactured by Toki Sangyo Co., Ltd.). It is preferably 5 to 500 mPa · S, specifically 5 to 500 mPa · S.

  As described above, the cured product of the curable resin composition of the present invention is obtained by impregnating a reinforced varnish composed of reinforcing fibers with a varnish in which the above-described components are uniformly mixed, and then in situ reaction. It is. Here, as described above, the in-situ reaction is performed simultaneously or continuously without distinguishing the reaction between the epoxy group and the acid group and the polymerization reaction of the radical polymerizable group as reaction steps. Is.

  Specifically, the curing temperature at the time of performing the in-situ reaction is preferably in the temperature range of 50 to 250 ° C., and in particular, after curing at 50 to 100 ° C. to obtain a tack-free cured product. Furthermore, it is preferable to perform the treatment under a temperature condition of 120 to 200 ° C.

  The curable resin composition described in detail above is a laminate for a printed wiring board, an interlayer insulating material for a build-up board, an adhesive film for a build-up, a semiconductor sealing material, a die attach agent, an underfill material for flip chip mounting, and a grab top. Resin materials used for electronic circuit boards such as materials, liquid sealing materials for TCP, conductive adhesives, liquid crystal sealing materials, flexible substrate coverlays, resist inks; optical materials such as optical waveguides and optical films, resins Coating materials such as casting materials, adhesives, insulating paints; various optical semiconductor devices such as LEDs, phototransistors, photodiodes, photocouplers, CCDs, EPROMs, photosensors; various fiber reinforced resin molded products such as CFRP It can be applied to any use. Among these, a laminate for a printed wiring board and a fiber reinforced resin molded product typified by CFRP are preferable from the viewpoint of having particularly excellent fluidity and high heat resistance.

  When the curable resin composition of the present invention is used for a laminated board for a printed wiring board, specifically, a varnish obtained by blending the above-described components is made of paper, glass cloth, glass nonwoven fabric, aramid paper, aramid A prepreg that is a cured product can be obtained by impregnating various fiber base materials such as cloth, glass mat, and glass roving cloth, and heating at a heating temperature according to the solvent type used, preferably 50 to 170 ° C. . The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Moreover, when manufacturing a copper clad laminated board using this epoxy resin composition, the prepreg obtained as mentioned above is laminated | stacked by a conventional method, copper foil is laminated | stacked suitably, and it is under pressure of 1-10 MPa. A copper-clad laminate can be obtained by thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours.

  Next, when the curable resin composition of the present invention is used in a fiber reinforced resin molded article, specifically, each component constituting the curable resin composition of the present invention is uniformly mixed to adjust the varnish, Next, after impregnating this with a reinforcing substrate made of reinforcing fibers, it is obtained by in-situ reaction. Here, as described above, the in-situ reaction is performed simultaneously or continuously without distinguishing the reaction between the epoxy group and the acid group and the polymerization reaction of the radical polymerizable group as reaction steps. Is.

  Specifically, the curing temperature at the time of performing the in-situ reaction is preferably in the temperature range of 50 to 250 ° C., and in particular, after curing at 50 to 100 ° C. to obtain a tack-free cured product. Furthermore, it is preferable to perform the treatment under a temperature condition of 120 to 200 ° C.

  In the present invention, since the varnish viscosity is significantly lower than that of the conventional CFRP varnish, the heating temperature when impregnating the varnish into the fiber reinforcing material is kept low, or the room temperature is 5 to 40 ° C. Impregnation in the region is possible. On the other hand, the molded product obtained by impregnating the fiber reinforcement and in-situ curing in spite of such a low viscosity varnish is not inferior to the conventional CFRP molded product in strength, but rather has a drastic heat resistance. The improvement is a notable point.

  The fiber-reinforced composite material of the present invention comprises the above-described resin composition for fiber-reinforced composite material and reinforcing fibers as essential components, and specifically, a varnish obtained by uniformly mixing the above-described components. That is, what is obtained by impregnating a reinforcing substrate made of reinforcing fibers with a resin composition for fiber-reinforced composite materials is mentioned.

  Here, the reinforcing fiber may be any of a twisted yarn, an untwisted yarn, or a non-twisted yarn, but the untwisted yarn or the untwisted yarn has both the moldability and mechanical strength of the fiber-reinforced plastic member, preferable. Furthermore, the form of a reinforced fiber can use what the fiber direction arranged in one direction, and a textile fabric. The woven fabric can be freely selected from plain weaving, satin weaving, and the like according to the site and use. Specifically, since it is excellent in mechanical strength and durability, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like can be mentioned, and two or more of these can be used in combination. Among these, carbon fiber is preferable from the viewpoint that the strength of the molded product is particularly good. As the carbon fiber, various types such as polyacrylonitrile-based, pitch-based, and rayon-based can be used. Among these, a polyacrylonitrile-based one that can easily obtain a high-strength carbon fiber is preferable. Here, the use amount of the reinforcing fiber when the varnish is impregnated into a reinforcing base material made of reinforcing fiber to form a fiber-reinforced composite material is such that the volume content of the reinforcing fiber in the fiber-reinforced composite material is 40 to 85%. The amount is preferably in the range.

  The fiber-reinforced resin molded product of the present invention is a molded product having a cured product of a resin composition for fiber-reinforced composite material and reinforcing fibers, specifically, the amount of reinforcing fibers in the fiber-reinforced resin molded product is: It is in the range of 40 to 70% by mass, and particularly preferably in the range of 50 to 70% by mass from the viewpoint of strength.

  As a method for producing such a fiber reinforced resin molded article, a fiber aggregate is laid on a mold, and a hand layup method or a spray-up method in which the varnish is laminated in multiple layers, either a male type or a female type, Vacuum bag method in which a base made of reinforcing fibers is stacked and impregnated while impregnating varnish, covered with a flexible mold that allows pressure to act on the molded product, and hermetically sealed is vacuum (reduced pressure) molding, reinforcing fibers in advance SMC press method in which a varnish containing varnish is formed into a sheet is compression-molded with a mold, RTM method in which the varnish is injected into a mating die laid with fibers, and a prepreg is produced by impregnating the varnish into a reinforcing fiber, There are methods such as baking this in a large autoclave. Among these, the RTM method is particularly preferred because of its excellent varnish fluidity. Preferred.

As a specific method for producing a fiber reinforced resin molded article by the RTM method, the production method of the present invention described in detail below is preferable.
That is, in the method for producing a fiber-reinforced resin molded article of the present invention, the varnish is injected and impregnated into a base material made of reinforcing fibers arranged in a mold, and then cured in situ.

  Examples of the base material made of reinforcing fibers include woven fabrics made of reinforcing fibers, knits, mats, and blades, and these are further laminated, shaped, and used by means such as binders and stitches. It may be used as a preform having a fixed form.

  Moreover, as a type | mold, the closed closed mold which consists of materials, such as iron, steel, aluminum, FRP, wood, gypsum, is mentioned.

  The manufacturing method of the present invention will be described in more detail. A substrate made of reinforcing fibers is shaped along the mold surface of the lower mold, the upper mold and the lower mold are clamped, and the varnish is placed in the mold. There is a method of injection and then in-situ curing under the above-described curing temperature conditions. At this time, it is preferable to apply a gel coat to the mold surface before disposing the base material made of reinforcing fibers on the mold surface of the lower mold, from the viewpoint of improving the appearance of the molded product. After curing, the desired fiber-reinforced resin molded product can be obtained by demolding. In the present invention, post-curing may be performed at a higher temperature after demolding.

  In addition to the reinforcing fiber substrate, a foam core, a honeycomb core, a metal part, and the like may be installed in the mold, and a composite material integrated with these may be used. In particular, a sandwich structure obtained by placing and molding carbon fiber substrates on both sides of a foam core is lightweight and has a large bending rigidity, and thus is useful as an outer plate material for automobiles, aircrafts and the like.

  Applications of the fiber-reinforced resin molded article thus obtained include sports equipment such as fishing rods, golf shafts, bicycle frames, automobiles, aircraft frames or body materials, spacecraft members, wind power generator blades, and the like. . In particular, since high heat resistance is required for automobile members, aircraft members, and spacecraft members, the fiber-reinforced resin molded article of the present invention is suitable for these applications.

  Among the various uses described above, for example, the curable resin composition of the present invention is used as an interlayer insulating material for a buildup substrate, and, for example, rubber, filler, etc. are appropriately blended to produce a buildup substrate. The cured curable resin composition is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. Such operations are sequentially repeated as desired, and a build-up substrate can be obtained by alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern.

  When the curable resin composition of the present invention is used as an underfill material for a semiconductor sealing material or flip chip mounting, it can be prepared by blending a filler with the curable resin composition. As the filler, silica is usually used, and the filling ratio is preferably in the range of 30 to 95% by mass per 100 parts by mass of the curable resin composition. Among them, flame retardancy and moisture resistance are preferred. In order to improve solder crack resistance and decrease the linear expansion coefficient, it is particularly preferably 70 parts by mass or more, and in order to significantly increase these effects, 80 parts by mass or more can further enhance the effect. it can.

  The method for producing an adhesive film for buildup from the curable resin composition of the present invention is, for example, a multilayer printed wiring board in which the curable resin composition of the present invention is applied on a support film to form a resin composition layer. And an adhesive film for use.

  In order to produce an optical semiconductor device from the curable resin composition of the present invention, for example, the curable resin composition is applied to an optical semiconductor to which an electrode such as a lead wire is attached, for example. Examples include a method of sealing and curing by a molding method such as transfer molding and casting, and a method of previously mounting an optical semiconductor on a circuit board, sealing it with the curable resin composition of the present invention, and curing. . Specifically, it can be obtained by pouring into a mold set with an optical semiconductor element, followed by heat curing under the above temperature conditions.

  As described above, the optical semiconductor device specifically includes an optical semiconductor device in which a light receiving element or a light emitting element such as an LED, a phototransistor, a photodiode, a photocoupler, a CCD, an EPROM, or a photosensor is sealed. Among them, an LED device, particularly a high-intensity LED device is particularly preferable, and a blue to white LED device having a main emission peak at a wavelength of 350 to 550 nm and a quaternary LED device are particularly preferable.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on weight unless otherwise specified. In addition, each physical property evaluation was measured on condition of the following.
1) Varnish viscosity: Measured at 25 ° C. using an E-type viscometer (“TV-20 type” cone plate type manufactured by Toki Sangyo Co., Ltd.).
2) Glass transition point (dynamic viscoelasticity measurement (DMA method)): The cured product was cut into a width of 5 mm and a length of 50 mm with a diamond cutter, and measured using “DMS6100” manufactured by SII Nanotechnology, Inc. Room temperature to 260 ° C., temperature rising rate: 3 ° C./min, frequency: 1 Hz (sine wave), strain amplitude: 10 μm, dynamic viscoelasticity due to double-end bending of the cured product was measured. The temperature at the maximum value of tan δ was defined as Tg.
3) Bending strength and flexural modulus of resin plate: compliant with JIS6911.
4) Bending strength of carbon fiber reinforced composite material: compliant with JISK7074.

[Laminated board]
1) Varnish viscosity: Measured at 30 ° C. using a B-type viscometer (“TVB-10 type viscometer” M type manufactured by Toki Sangyo Co., Ltd.).
2) Dynamic viscoelasticity measurement (DMA): A cured product is cut into a width of 5 mm and a length of 50 mm with a diamond cutter, and measured using “DMS6100” manufactured by SII Nanotechnology, Inc. Measurement temperature range: room temperature to 300 ° C., rising Temperature rate: 3 ° C./min, frequency: 1 Hz (sinusoidal wave), strain amplitude: 10 μm, dynamic viscoelasticity due to double-end bending of the cured product was measured. The temperature at the maximum value of tan δ was defined as Tg.

Synthesis example 1
In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 240 parts (1.50 mol) of 2,7-dihydroxynaphthalene and 85 parts (1.05 mol) of 37% by weight formaldehyde aqueous solution Then, 376 parts of isopropyl alcohol and 88 parts (0.75 mol) of 48% potassium hydroxide aqueous solution were charged, and stirred at room temperature while blowing nitrogen. Then, it heated up at 75 degreeC and stirred for 2 hours. After completion of the reaction, 108 parts of first sodium phosphate was added for neutralization, isopropyl alcohol was removed under reduced pressure, and 480 parts of methyl isobutyl ketone was added. The obtained organic layer was repeatedly washed with 200 parts of water three times, and then methyl isobutyl ketone was removed by heating under reduced pressure to obtain 245 parts of a phenol compound (A-1). The obtained compound (A-1) had a hydroxyl equivalent of 84 grams / equivalent. A peak indicating that a carbonyl group was generated in the vicinity of 203 ppm was detected from the C ¹³ NMR chart, and the following structural formula was obtained from the MS spectrum.

で表される原料フェノールを示す３４４のピークが検出された。

The peak of 344 which shows the raw material phenol represented by this was detected.

Next, 84 parts by mass (1.0 equivalent of hydroxyl group) of the phenol compound (A-1) obtained by the above reaction while purging a flask equipped with a thermometer, a condenser, and a stirrer with nitrogen gas purge, 463 parts of epichlorohydrin (5. 0 mol) and 53 parts of n-butanol were charged and dissolved. After the temperature was raised to 50 ° C., 220 parts by mass of a 20% aqueous sodium hydroxide solution (1.10 mol) was added over 3 hours, and the reaction was further continued at 50 ° C. for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. 300 parts of methyl isobutyl ketone and 50 parts of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 15 parts of a 10% by mass sodium hydroxide aqueous solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 100 parts of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 126 parts of the desired epoxy resin (A-2). The resulting epoxy resin (A-2) has a softening point of 95 ° C. (based on “JIS-K2531”. Softening point by ring and ball method (B & R method)), melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) was 9.0 dPa · s, and the epoxy equivalent was 170 g / equivalent. A peak indicating that a carbonyl group was generated in the vicinity of 203 ppm was detected from the C ¹³ NMR chart, and a 512 peak representing the following structural formula (i-α) was detected from the MS spectrum.

  The epoxy resin (A-2) is composed of 10.5% by mass of the compound represented by the structural formula (i-α), and the following structural formula (i-β).

で表される化合物を３９．６質量％、その他オリゴマー成分を４９．９質量％含有するものであった。

39.6% by mass of the compound represented by the formula, and 49.9% by mass of other oligomer components.

Examples 1-3
1. Epoxy resin composition blending According to the blending shown in Table 1 below, an epoxy resin and a carboxylic acid, a polymerizable compound, a radical polymerization initiator, a curing accelerator, and the like were blended using a stirrer to obtain an epoxy resin composition. . Varnish viscosity was evaluated using this epoxy resin composition.
2. Preparation of cured resin plate of epoxy resin An epoxy resin composition was poured into a mold gap in which a spacer (silicone tube) having a thickness of 2 mm was sandwiched between glass plates, and cured in an oven at 100 ° C. for 1 hour. After confirming that it was in a tack-free state, after-curing was further performed at 170 ° C. for 1 hour to obtain a cured resin plate having a thickness of 2 mm. Using this as a test piece, various evaluation tests were performed. The results are shown in Table 1.
3. Production of Carbon Fiber Reinforced Composite Material Carbon fiber fabric (carbon fiber: CO6343, cut out to 150 mm × 150 mm on a SUS plate coated with a 200 mm × 200 mm × 3.5 mm polytetrafluoroethylene / perfluoroalkyl vinyl ether copolymer. 4 sheets of a basis weight of 198 g / cm ² , manufactured by Toray Industries, Inc., cast the epoxy resin composition and impregnate the resin by pressing the resin with a roller, and another polytetrafluoroethylene / perfluoro A SUS plate coated with an alkyl vinyl ether copolymer was placed. This was after-cured in an oven at 100 ° C. for 1 hour and then at 170 ° C. for 1 hour to obtain a fiber-reinforced composite material having a thickness of 1.5 mm. Voids such as bubbles were not confirmed in the fiber-reinforced composite material obtained by visual confirmation. Using this as a test piece, various evaluation tests were performed. The results are shown in Table 1.

Comparative Examples 1 and 2
1. Epoxy resin composition blending In accordance with the blending shown in Table 2 below, each component was blended and blended using a stirrer to obtain an epoxy resin composition. Varnish viscosity was evaluated using this epoxy resin composition.
2. Preparation of cured resin plate of epoxy resin composition The epoxy resin composition was poured into the gaps of the molds used in the examples and cured in an oven at 100 ° C for 4 hours to obtain a cured resin plate having a thickness of 2 mm. Using this as a test piece, various evaluation tests were performed. The results are shown in Table 1.
3. Preparation of Carbon Fiber Reinforced Composite Material Four carbon fiber fabrics were laminated in the same manner as in the example, and the epoxy resin composition was cast and the resin was impregnated by pressing the resin with a roller. A SUS plate coated with a fluoroethylene / perfluoroalkyl vinyl ether copolymer was placed and after-cured in an oven at 100 ° C. for 1 hour and then at 170 ° C. for 1 hour. In addition to insufficient impregnation of the carbon fiber, the carbon fiber was exposed on the surface, and there were many bubbles on the resin part and the surface, making it impossible to produce a test piece that could withstand the evaluation test.

In addition, each component used for the epoxy resin composition of an Example and a comparative example is as follows.
“Epoxy resin (A-2)”: Epoxy resin obtained in Synthesis Example 1 “HP-4032”: Naphthalene type epoxy resin, trade name “EPICLON HP-4032” manufactured by DIC Corporation, epoxy equivalent 150 g / eq, Semi-solid “850S”: bisphenol A type liquid epoxy resin, trade name “EPICLON 850S” manufactured by DIC Corporation, epoxy equivalent of 188 g / eq
“830”: bisphenol F type liquid epoxy resin, trade name “EPICLON 830” manufactured by DIC Corporation, epoxy equivalent of 171 g / eq
“Perhexa HC”: 1,1-di (t-hexylperoxy) cyclohexane, trade name “Perhexa HC” manufactured by NOF Corporation “2E4MZ”: 2-ethyl-4-methylimidazole “Aromatic polyamine” : Diethyltoluenediamine, trade name “ETHACURE-100” amine-based curing agent manufactured by PTI Japan Ltd. “Lewis acid catalyst A”: boron trifluoride tetrahydrofuran complex “Lewis acid catalyst B”: trifluoride Boron diethyl ether complex

Comparative Example 3
242 g of methacrylic acid is charged into a four-necked flask, 0.4 g of hydroquinone is added, and then heated to 100 ° C., and 600 g of o-cresol novolac type epoxy resin (DIC made Epiklon N-695, epoxy equivalent: 214) is added. Slowly add and dissolve, then add 1.68 g of triphenylphosphine and react at 120-125 ° C. for 3 hours. After completion of the reaction, 292 g of styrene was added and dissolved uniformly with slow cooling to obtain a resin solution.
150 g of the resin solution thus obtained was added to 1.5 g of 1-cyanoethyl-2-ethyl-4-methylimidazole (“2E4MZ-CN” manufactured by Shikoku Chemicals Co., Ltd.), 1,1-di (t- 1.5 g of hexylperoxy) cyclohexane (“Perhexa HC” manufactured by NOF Corporation) was added and stirred and mixed at room temperature to obtain a varnish with a solid content of 82% by mass, and the viscosity of this varnish was measured.

Next, the obtained varnish was poured into a mold gap in which a spacer (silicone tube) having a thickness of 3 mm was sandwiched between glass plates, heated at 100 ° C. for 1 hour, and then heated at 200 ° C. for 1 hour to obtain a cured product. The dynamic viscoelasticity was measured by the above method and Tg was determined.
The varnish viscosity and Tg values are shown in Table 2.

Comparative Example 4
78.8 g of bisphenol A type epoxy resin (“Epiclon 850S” manufactured by DIC Corporation, epoxy equivalent of 188 g / eq.), Methyltetrahydrophthalic anhydride (“Epiclon B-570” manufactured by DIC Corporation, equivalent of 166 g / eq) .) 71.3 g and dimethylbenzylamine 1.5 g were uniformly stirred and mixed using a stirrer to obtain a varnish having a solid concentration of 52% by mass, and the viscosity of the varnish was measured.
Next, the obtained varnish was poured into a mold gap in which a spacer (silicone tube) having a thickness of 3 mm was sandwiched between glass plates, held at 110 ° C. for 1 hour to be cured, and the cured product was taken out of the mold. The temperature was raised to 165 ° C., and after reaching 165 ° C., curing was carried out by holding at that temperature for 2 hours. Using the obtained cured product as a test piece, dynamic viscoelasticity was measured to obtain Tg.
The varnish viscosity and Tg values are shown in Table 2.

Comparative Example 5
105 g of dimethacrylate of bisphenol A type epoxy resin (“Epiclon 850S” epoxy equivalent of 188 g / eq. Manufactured by DIC Corporation), 45 g of styrene monomer, 1,1-di (t-hexylperoxy) cyclohexane (manufactured by NOF Corporation “ Perhexa HC ") 1.5 g was uniformly mixed using a stirrer to obtain a varnish having a solid concentration of 69% by mass, and the viscosity of the varnish was measured.
Next, the obtained varnish was poured into a gap of a mold in which a spacer (silicone tube) having a thickness of 3 mm was sandwiched between glass plates, held at 100 ° C. for 1 hour to be cured, and the cured product was taken out of the mold. The temperature was raised to 170 ° C., and after reaching 170 ° C., curing was carried out by holding at that temperature for 1 hour. Using the obtained cured product as a test piece, dynamic viscoelasticity was measured to obtain Tg.
The varnish viscosity and Tg values are shown in Table 2.

Claims (13)

Polyfunctional epoxy resin containing a naphthalene skeleton in the molecular structure (A), a molecular weight of 300 or less acid group-containing radical polymerizable monomer (B), LA radical polymerization initiator (C), wherein the acid group-containing radical polymerization Other radical polymerizable monomer (D) and carbon fiber as essential components , the epoxy group in the epoxy resin (A) and the acid group-containing radical polymerizable monomer The equivalent ratio [epoxy group / acid group] with the acid group in the body (B) is a ratio of 1/1 to 1 / 0.1, and the acid group-containing radical polymerizable monomer (B), In-situ polymerization in which the mass ratio of the acid group-containing radical polymerizable monomer (B) to the other radical polymerizable monomer (D) is in the range of [the former / the latter] = 20/80 to 80/20 Fiber reinforced composite material for reaction . The acid group-containing radical polymerizable monomer (B) having a molecular weight of 300 or less is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and anhydrides thereof. Item 1. A fiber-reinforced composite material for in situ polymerization reaction according to Item 1. The fiber-reinforced composite material for in-situ polymerization reaction according to claim 1 or 2, wherein the content of the radical polymerization initiator (C) per 100 parts by mass of the composition is 0.1 to 3 parts by mass . The fiber-reinforced composite material for in-situ polymerization reaction according to claim 1, wherein the polyfunctional epoxy resin (A) containing a naphthalene skeleton in the molecular structure has a softening point of 100 ° C or lower. Fiber-reinforced composite material according to claim 1, wherein the volume content of the carbon fibers is in the range 40 to 85%. The fiber-reinforced composite material for in-situ polymerization reaction according to any one of claims 1 to 3 , further comprising an epoxy resin curing agent in addition to the above components. Hardened | cured material obtained by carrying out the in-situ polymerization reaction of the fiber reinforced composite material as described in any one of Claims 1-6 . The resin composition for printed wiring boards which consists of a fiber reinforced composite material as described in any one of Claims 1-6. A fiber-reinforced resin molded product comprising a cured product of the fiber-reinforced composite material according to any one of claims 1 to 6 as an essential component. The fiber-reinforced resin molded article according to claim 9 , wherein the volume content of the reinforcing fibers is in the range of 40 to 85%. The fiber reinforced composite material according to any one of claims 1 to 6 is injected into a substrate made of reinforcing fibers arranged in a mold, impregnated, and then cured by in situ polymerization reaction. A method for producing a fiber-reinforced resin molded product characterized by the above. The inside of a mold cavity in which a substrate made of reinforcing fibers is disposed is depressurized, and the fiber-reinforced composite material according to any one of claims 1 to 6 is used by utilizing a pressure difference between the decompressed internal pressure of the cavity and external pressure. It was injected into the cavity Te, a vacuum RTM molding method of impregnating the base material, a manufacturing method of claim 1 1, wherein the fiber-reinforced resin molded article. The fiber-reinforced resin molded article according to claim 9 or 10 , which is an automobile member.