JP2021075652A - Curable resin composition, and film, molding, prepreg and fiber-reinforced plastic including the same - Google Patents

Abstract

To provide a curable resin composition that gives excellent fracture strength when applied to a composite material, a prepreg including the resin composition, and a fiber-reinforced plastic formed using the prepreg.SOLUTION: A prepreg contains a reinforced fiber and a matrix resin. The matrix resin contains the following components: (A) bisphenol-type epoxy resin with a softening point of 80°C or higher, (B) bisphenol-type epoxy resin that is liquid at 25°C, (C1) a di-functional or multi-functional (meth)acrylate having a cyclic structure, (C2) (meth)acrylate having an open-chain structure, and (D) a curing agent.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition, and a film, molded product, prepreg, and fiber reinforced plastic using the curable resin composition, and is suitably used for sports / leisure applications, general industrial applications, aircraft material applications, and the like. It is a thing.

Since fiber reinforced plastics are lightweight, have high strength, and have high rigidity, they are widely used from sports / leisure applications to industrial applications such as automobiles and aircraft. Fiber reinforced plastics can be obtained by using a prepreg in which a reinforcing material made of continuous fibers such as reinforcing fibers is impregnated with a matrix resin. Further, a molded product can be obtained by laminating a plurality of prepregs and curing them by heating. Due to the need for weight reduction in many fields, carbon fiber is often used as a reinforcing fiber from the viewpoint of strength elastic modulus, and epoxy resin is often used as a matrix resin from the viewpoint of adhesion to carbon fiber. With respect to the strength and weight of molded products, commonly used epoxy resins are brittle and have low toughness after curing, so improvement of the fracture toughness and rigidity of the fiber reinforced plastic is required. It was.

In response to this problem, Patent Document 1 uses a specific epoxy resin and a radically polymerizable monomer as a matrix resin to form a cured resin product having excellent strength, elasticity and toughness, and has excellent mechanical properties. It has been found that a fiber-reinforced plastic can be obtained (Patent Document 1).

International Publication No. 2018/11214

In the technique disclosed in Patent Document 1, the strain during the resin bending test is not sufficient, and the adhesiveness to the medium elastic carbon fiber is low, so that the 90 ° bending strength of the fiber reinforced plastic tends to decrease. There was a tendency. The present invention is formed by using a curable resin composition capable of obtaining excellent breaking strength, particularly when applied to a tubular composite material, a prepreg using the resin composition, and further using this prepreg. It provides fiber reinforced plastics.

The present invention has been made in view of the above background, and by using a (meth) acrylate having a cyclic structure and a (meth) acrylate having a chain structure in combination, the rigidity and strain of the curable resin composition can be increased. It was found that a fiber reinforced plastic having excellent mechanical properties can be obtained. That is, the present invention relates to the following.
[1] A prepreg containing carbon fibers and a matrix resin, wherein the matrix resin contains the following components (A), (B), (C1), (C2), and (D).
Component (A): Bisphenol type epoxy resin with a softening point of 80 ° C or higher,
Ingredient (B): Bisphenol type epoxy resin liquid at 25 ° C,
Component (C1): (meth) acrylate having a cyclic structure,
Component (C2): (Meta) acrylate component having a chain structure (D): Curing agent.
[2] The prepreg according to [1], wherein the matrix resin contains a compound having a component (E): polysiloxane structure.
[3] The prepreg according to [1] or [2], wherein the matrix resin contains a component (H): an oxazolidone type epoxy resin.
[4] At least one partial structure in which the component (C1) is selected from the group consisting of a molecular structure including a benzene skeleton, an isocyanuric acid skeleton, a dicyclopentadiene skeleton, a biphenyl skeleton, a phenylbenzoate skeleton, an azobenzene skeleton, and a stilbene skeleton. The prepreg according to any one of [1] to [3].
[5] Any one of [1] to [4], wherein the component (C1) is an ethoxylated isocyanuric acid triacrylate, a tricyclodecanedimethanol diacrylate, or a bisphenol A diglycidyl ether acrylic acid adduct. The prepreg described in.
[6] The prepreg according to any one of [1] to [5], wherein the component (C2) is pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate.
[7] The prepreg according to any one of [1] to [6], wherein the content mass ratio (C1 / C2) of the component (C1) and the component (C2) is 2.0 or more and 20 or less. ..
[8] A curable resin composition containing the following components (A1), (C1), (C2), and (D).
Ingredient (A1): Epoxy resin,
Component (C1): (meth) acrylate having a cyclic structure,
Component (C2): (Meta) acrylate component having a chain structure (D): Curing agent.
[9] The component (C1) of the curable resin composition is selected from the group consisting of a molecular structure including a benzene skeleton, an isocyanuric acid skeleton, a dicyclopentadiene skeleton, a biphenyl skeleton, a phenylbenzoate skeleton, an azobenzene skeleton, and a stilbene skeleton. The curable resin composition according to [8], which has at least one partial structure.
[10] The curable resin composition according to [8] or [9], wherein the component (A1) contains the following components (A) and (B).
Component (A): Bisphenol type epoxy resin with a softening point of 80 ° C or higher,
Ingredient (B): A bisphenol type epoxy resin that is liquid at 25 ° C.
[11] The curable resin composition according to any one of [8] to [10], wherein the curable resin composition contains the component (H): oxazolidone type epoxy resin.
[12] A component (d1) in which the component (D) is at least one selected from the group consisting of dicyandiamides, ureas, imidazoles, and aromatic amines, and a component (d2) which is a radical polymerization initiator. The curable resin composition according to any one of [8] to [11], which comprises.
[13] The curable resin composition according to [12], wherein the component (d1) is contained in an amount of 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the curable resin composition.
[14] The component (d2) is contained in an amount of 0.1 part by mass or more and 5 parts by mass or less with respect to a total of 100 parts by mass of all (meth) acrylate compounds contained in the curable resin composition, [12] or [ 13] The curable resin composition.
[15] The curable resin composition according to [10], wherein the component (A) is contained in an amount of 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the curable resin composition.
[16] The curable resin composition according to [10], wherein the component (B) is contained in an amount of 20 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the curable resin composition.
[17] The components (C1) and (C2) are contained in a total of 5 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the curable resin composition [8] to [16]. The curable resin composition according to any one of the above.
[18] The curing according to any one of [8] to [17], wherein the content mass ratio (C1 / C2) of the component (C1) and the component (C2) is 2.0 or more and 20 or less. Sex resin composition.
[19] The curable resin composition according to any one of [8] to [18], which comprises a thermoplastic resin.
[20] The curable resin composition according to [19], wherein the component (I) is contained in an amount of 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the curable resin composition.
[21] A film formed from the curable resin composition according to any one of [8] to [20].
[22] The cured product of the curable resin composition according to any one of [8] to [20].
[23] A prepreg in which an aggregate of reinforcing fibers is impregnated with the curable resin composition according to any one of [8] to [20].
[24] A fiber-reinforced plastic comprising a cured product of the curable resin composition according to any one of [8] to [20] and reinforcing fibers.
[25] The fiber-reinforced plastic according to [24], wherein the reinforcing fiber is carbon fiber.
[26] The fiber reinforced plastic according to [24] or [25], which is tubular.

The curable resin composition of the present invention enhances the rigidity and strain of the cured resin, and a fiber reinforced plastic having excellent mechanical characteristics can be obtained.

Hereinafter, the present invention will be described in detail.
In the present invention, the "epoxy resin" means a compound having two or more epoxy groups in one molecule, and the "bifunctional or higher (meth) acrylate compound" means two in one molecule. It means an acrylate compound (acrylic acid ester) and / or a methacrylate compound (methacrylic acid ester) having two or more double bonds. The "curable resin composition" means a resin composition containing an epoxy resin, (meth) acrylate compounds, a curing agent, a curing accelerator, and in some cases, a thermoplastic resin, an additive, or the like. To do. In the present invention, a cured product obtained by curing a curable resin composition is referred to as a "resin cured product", and among them, a plate-shaped cured product may be referred to as a "resin plate". In the present invention, the softening point, the epoxy equivalent, and the active hydrogen equivalent are values measured under the following conditions. That is, the softening point is a value measured according to JIS-K7234: 2008 (ring ball method). Epoxy equivalent is a value measured according to JIS K-7236: 2001. The active hydrogen equivalent is a value measured according to JIS K-7237: 1995.

[Curable resin composition]
One of the aspects of the curable resin composition of the present invention (hereinafter, also referred to as "the present resin composition") includes a component (A1), a component (C1), a component (C2), and a component (D). .. Further, a component (C), a component (E), a component (H), a component (I), a component (F), a component (G), and an additive as an optional component may be contained.

<Ingredient (A1)>
As the component (A1), any epoxy resin can be used as long as it is an epoxy resin. Specifically, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, an epoxy resin having an oxazolidone ring skeleton, and a novolak type epoxy resin. , Triglycidylaminophenol, tetraglycidyldiaminodiphenylmethane, hydrophthalic acid type epoxy resin, bisphenol S type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, bisphenoloxyethanol fluorene type epoxy resin, bisphenol fluorene type epoxy resin, bisphenol fluorene type Epoxy resin and the like can be mentioned. Among these, one or more epoxy resins selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin having an oxazolidone ring skeleton, novolac type epoxy resin, triglycidyl aminophenol, and tetraglycidyl diaminodiphenylmethane are preferable. As the component (A1), it is preferable to use (A) and / or (B) described later. In particular, by combining a plurality of these epoxy resins, it is possible to obtain a prepreg having excellent handleability and more controllable resin flow during molding, and a carbon fiber reinforced composite material having excellent mechanical properties and heat resistance. ..

<Ingredient (A)>
The component (A) is a bisphenol type epoxy resin having a softening point of 80 ° C. or higher. The softening point is preferably 82 ° C. or higher, more preferably 85 ° C. or higher, because the cured resin product has excellent toughness. On the other hand, it is preferable because the heat resistance of the cured resin product is properly maintained, a prepreg having excellent tack and drape properties (mold shape followability) can be obtained, and a fiber-reinforced composite material without voids can be obtained. Is 150 ° C. or lower, more preferably 145 ° C. or lower.

The present resin composition preferably contains the component (A) in an amount of 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the present resin composition. The lower limit of the content of the component (A) is more preferably 13 parts by mass or more, and further preferably 15 parts by mass or more. The upper limit of the content of the component (B) is more preferably 60 parts by mass or less, and further preferably 40 parts by mass or less. The total epoxy resin is, for example, the total of the epoxy resins as the component (A) and the component (B), or when the resin composition further contains the component (F) and / or the component (H) described later. , The total of the epoxy resins as the component (A), the component (B), the component (F) and / or the component (H).

When the content of the component (A) in the present resin composition is at least the lower limit value, a cured resin product having excellent toughness can be obtained. On the other hand, when the content of the component (A) is not more than the upper limit value, the heat resistance of the cured resin product is properly maintained, and a prepreg having excellent tack and drape properties (mold shape followability (suppleness)) can be obtained. It is possible to obtain a fiber-reinforced composite material without voids.

As the component (A), a commercially available product may be used. The bisphenol A type epoxy resin having a softening point of 80 ° C. or higher that can be obtained as a commercially available product is not limited to these, but is limited to jER1055, jER1004, jER1007, and jER1009 (trade names, all manufactured by Mitsubishi Chemical Corporation), EPICLON2050, and EPICLON3050. , EPICLON4050, EPICLON7050, EPICLON HM-091, EPICLON HM-101 (all trade names, manufactured by DIC Corporation), YD-902, YD-903N, YD-904, YD-907, YD-7910, YD-6020 ( All of them have product names, manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation), etc. The bisphenol F type epoxy resin having a softening point of 80 ° C. or higher that can be obtained as a commercially available product is not limited to these, but is limited to jER4004P, jER4005P, jER4007P, jER4010P (trade name, manufactured by Mitsubishi Chemical Co., Ltd.) and YDF2004. , YDF-2005RD (both trade names, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) and the like. As the component (A), one of these may be used alone, or two or more thereof may be used in combination.

<Ingredient (B)>
The component (B) is a bisphenol type epoxy resin that is liquid at 25 ° C. The component (B) mainly contributes to the improvement of the strength, elastic modulus, and heat resistance of the cured resin product of the present resin composition. Here, "liquid" means that the bisphenol type epoxy resin exhibits fluidity. The viscosity of the bisphenol type epoxy resin liquid at 25 ° C. is preferably 500 Pa · s or less, and more preferably 300 Pa · s or less at 25 ° C. Further, it is preferably 0.1 Pa · s or more. When the viscosity is set in this range, the workability of the present resin composition can be improved. The viscosity can be measured by the method described in Examples.

The present resin composition preferably contains the component (B) in an amount of 20 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the present resin composition. The lower limit of the content of the component (B) is more preferably 25 parts by mass or more, and further preferably 28 parts by mass or more. The upper limit of the content of the component (B) is more preferably 75 parts by mass or less, further preferably 70 parts by mass or less, and particularly preferably 50 parts or less. When the content of the component (B) in the present resin composition is at least the lower limit value, a cured resin product having excellent strength and elastic modulus can be obtained. On the other hand, when the content of the component (B) is not more than the upper limit value, a cured resin product having excellent toughness can be obtained.

As the component (B), a commercially available product may be used. The commercially available bisphenol A type epoxy resin (component (B)) liquid at 25 ° C. is not limited to these, but jER827 (epoxy equivalent 185 g / eq), jER828 (epoxy equivalent 189 g / eq) ( YD-127 (epoxy equivalent 185 g / eq), YD-128 (epoxy equivalent 189 g / eq) (above, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), EPICLON840 (epoxy equivalent 185 g / eq), EPICLON850 (epoxy equivalent 189 g / eq) (above, manufactured by DIC Co., Ltd.), D.I. E. R331 (epoxy equivalent 187 / eq), D.I. E. Examples thereof include R332 (epoxy equivalent 173 g / eq) (manufactured by THE DOWN CHEMICAL COMPANY). The bisphenol F type epoxy resin (component (B)) having an epoxy equivalent of 250 or less that can be obtained as a commercially available product is not limited to these, but is limited to jER806 (epoxy equivalent 165 g / eq) and jER807 (epoxy equivalent 170 g / eq) (epoxy equivalent 170 g / eq). Above, Mitsubishi Chemical Co., Ltd.), YDF-170 (epoxy equivalent 170 g / eq) (Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), EPICLON830 (epoxy equivalent 170 g / eq), EPICLON835 (epoxy equivalent 172 g / eq) (above, DIC stock Made by the company), D.I. E. Examples thereof include R354 (epoxy equivalent 170 g / eq) (all manufactured by THE DOWN CHEMICAL COMPANY). One of these may be used alone, or two or more thereof may be used in combination.

<Component (C)>
The component (C) is a (meth) acrylate compound, and is preferably a bifunctional or higher functional (meth) acrylate compound from the viewpoint of strength and toughness. As the component (C), it is preferable to include a component (C1): a (meth) acrylate having a cyclic structure and a component (C2): a (meth) acrylate having a chain structure. It is assumed that the component (C1) and the component (C2) have different structures. Having a cyclic structure means having a cyclic structure such as benzene or cyclohexane in the molecule. Having a chain structure means having a carbon chain structure having 2 or more carbon atoms in the molecule. Among them, it is preferable to have a branched chain structure, and having a branched chain structure means that when the longest carbon chain among the carbon chain structures is the main chain, the carbon chain that branches and extends from the main chain is defined. Refers to having. Further, the component (C2) preferably has a non-cyclic structure having no cyclic structure. Since the component (C1) has a cyclic structure and a rigid skeleton, it contributes to the improvement of the elastic modulus of the cured resin of the resin composition, and the component (C2) has a flexible structure, so that the resin is present. It contributes to the improvement of the toughness of the cured resin product of the composition. By simultaneously containing (C1) and the component (C2), the elastic modulus and toughness of the present resin composition are improved, so that a cured resin product having high strength can be obtained.

Examples of the bifunctional (meth) acrylate compound of the component (C1) include diols such as tricyclodecanedimethanol, cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, bisphenoxyfluorene ethanol, and biphenol, and ethylene oxide in these diols. Examples thereof include di (meth) acrylates obtained by esterifying diols obtained by adding propylene oxide or caprolactone with (meth) acrylic acid.

Examples of the bifunctional (meth) acrylate compound of the component (C2) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and 1,3-butylene glycol. Lu, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol , 1,9-Nonandiol, 2-Methyl-1,8-octanediol, 1,10-decanediol, neopentyl glycol dioxane glycol of hydroxypivalate, etc., and ethylene oxide, propylene oxide or caprolactone to these diols. Examples thereof include di (meth) acrylates obtained by esterifying the added diols by reacting them with (meth) acrylic acid.

As the trifunctional (meth) acrylate compound of the component (C1), alcohols obtained by adding ethylene oxide, propylene oxide, caprolactone or the like to triol such as tris (2-hydroxyethyl) isocyanurate or p-aminophenol. Examples thereof include tri (meth) acrylates obtained by esterifying the mixture with (meth) acrylic acid. As the trifunctional (meth) acrylate compound of the component (C2), alcohols obtained by adding ethylene oxide, propylene oxide, caprolactone or the like to triol or tetraol such as trimethylolpropane, glycerol or pentaerythritol are used (meth). ) Examples thereof include tri (meth) acrylates obtained by esterification by reacting with acrylic acid.

Examples of the tetrafunctional or higher functional (meth) acrylate compound of the component (C2) include polyols such as ditrimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol, and ethylene oxide, propylene oxide, or caprolactone added to these polyols. Examples thereof include poly (meth) acrylates obtained by esterifying the obtained polyols with (meth) acrylic acid.

The components (C1) include 1,3- and 1,4-diisocyanatocyclohexane, 4,4'-methylene dicyclohexyl diisocyanate, 2,4-methylene dicyclohexyl diisocyanate, 2,2'-methylene dicyclohexyl diisocyanate, and tolylene diisocyanate. At least one of polyisocyanates such as isocyanate, diphenylmethane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate and hexamethylene diisocyanate as the component (C2), hydroxyethyl (meth) acrylate and hydroxypropyl ( Examples thereof include urethane poly (meth) acrylates obtained by directly adding meta) acrylate, pentaerythritol triacrylate and the like, and acrylates having a molecular structure including a phenylbenzoate skeleton, an azobenzene skeleton, and a stillben skeleton. ..

Among these, the component (C1) is preferably a bifunctional or higher functional (meth) acrylate having a cyclic structure from the viewpoint of elastic modulus. Further, from the viewpoint of elasticity, it has at least one partial structure selected from the group consisting of a molecular structure including a benzene skeleton, an isocyanuric acid skeleton, a dicyclopentadiene skeleton, a biphenyl skeleton, a phenylbenzoate skeleton, an azobenzene skeleton, and a stilbene skeleton. Is preferable. Specifically, ethoxylated isocyanuric acid triacrylate, tricyclodecanedimethanol diacrylate, or bisphenol A diglycidyl ether acrylic acid adduct and their caprolactone-modified or ethylene oxide-modified products are preferable. From the viewpoint of toughness, the component (C2) is preferably a (meth) acrylate having 2 or more and 4 or less functional groups, and specifically, pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate. ..
It is preferable to select the component (C1) and the component (C2) having low volatility so as not to volatilize in the step of preparing the carbon fiber composite material intermediate material. From the viewpoint of volatility, the molecular weight of the monomer is preferably 200 or more, and more preferably 250 or more. From the viewpoint of handleability, the molecular weight of the monomer is preferably 3000 or less, and more preferably 2000 or less. One of the listed components (C1) and (C2) may be used alone, or two or more of each may be used in combination.

The present resin composition preferably contains the component (C) in an amount of 5 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the present resin composition. The lower limit of the content of the component (C) is more preferably 10 parts by mass or more. The upper limit of the content of the component (C) is more preferably 40 parts by mass or less. The total amount of the component (C1) and the component (C2) is the same as the preferable content of the component (C). When the content of the component (C) in the present resin composition is at least the lower limit value, a cured resin product having excellent strength and elastic modulus tends to be obtained. On the other hand, when the content of the component (C) is not more than the upper limit value, a cured resin product having excellent dimensional stability tends to be obtained. The mass ratio (C1 / C2) of the component (C1) and the component (C2) is preferably 2.0 or more, more preferably 3.0 or more, from the viewpoint of elastic modulus. From the viewpoint of toughness, 20 or less is preferable, and 10 or less is more preferable.

<Component (D)>
Component (D) is a curing agent. The curing agent used as the component (D) is not particularly limited, but it is preferable to use the component (d1) that cures the components (A) and (B) and the component (d2) that cures the component (C) in combination. As the component (d1), dicyandiamides, ureas, imidazoles, aromatic amines, other amine-based curing agents, acid anhydrides, boron chlorideamine complexes and the like can be used, and in particular, dicyandiamides, ureas and imidazoles. , It is preferable to use at least one curing agent selected from aromatic amines.

Since dicyandiamide has a high melting point and its compatibility with an epoxy resin is suppressed in a low temperature region, it is preferable to use it as a curing agent (d1) because a curable resin composition having an excellent pot life tends to be obtained. Further, it is preferable that the curable resin composition contains dicyandiamide as the curing agent (d1) because the mechanical properties of the cured resin composition tend to be improved.

The content of dicyandiamide in the curable resin composition of the present invention is such that the number of moles of active hydrogen of dicyandiamide is 0.4 to the total number of moles of epoxy groups contained in the epoxy resin contained in this curable resin composition. The amount is preferably 1 times. By setting the value to 0.4 times or more, a cured product having good heat resistance and good mechanical properties (that is, high strength and elastic modulus) tends to be obtained. Further, by setting the value to 1 times or less, there is an advantage that a cured product having good mechanical properties (that is, excellent in plastic deformation ability and impact resistance) tends to be obtained. Further, by increasing the number of moles of active hydrogen of this dicyandiamide to 0.5 to 0.8 times, the heat resistance of the cured resin product tends to be more excellent, which is more preferable. Examples of commercially available dicyandiamides include, but are not limited to, DICY7, DICY15 (all manufactured by Mitsubishi Chemical Corporation), and DICYANEX1400F (manufactured by Air Products & Chemicals).

The ureas used as the component (d1) have a dimethylureido group in the molecule and generate an isocyanate group and a dimethylamine by heating at a high temperature, and these are the epoxy groups of the component (A) and the component (B). Or, as long as it activates an epoxy resin to be used in combination, the present invention is not particularly limited. For example, an aromatic dimethylurea in which a dimethylureido group is bonded to an aromatic ring and an aliphatic dimethylurea in which a dimethylureido group is bonded to an aliphatic compound. Etc. can be given. Among these, aromatic dimethylurea is preferable in that the curing rate tends to be high and the heat resistance and bending strength of the cured product tend to be high.

As the aromatic dimethylurea, for example, phenyldimethylurea, methylenebis (phenyldimethylurea), trilenbis (dimethylurea) and the like are preferably used. Specific examples include 4,4'-methylenebis (phenyldimethylurea) (MBPDMU), 3-phenyl-1,1-dimethylurea (PDMU), 3- (3,4-dichlorophenyl) -1,1-dimethylurea. (DCMU), 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea, 2,4-bis (3,3-dimethylureido) toluene (TBDMU), m-xylylene diisocyanate and dimethylamine Examples include dimethylurea obtained from. Among these, DCMU, MBPDMU, TBDMU, and PDMU are more preferable from the viewpoint of curing acceleration ability and imparting heat resistance to the cured resin product. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the aliphatic dimethylurea include dimethylurea obtained from isophorone diisocyanate and dimethylamine, and dimethylurea obtained from hexamethylene diisocyanate and dimethylamine. Further, as the ureas, commercially available products may be used. Examples of commercially available DCMU products include, but are not limited to, DCMU-99 (all manufactured by Hodogaya Chemical Co., Ltd.). Examples of commercially available MBPDMU products include, but are not limited to, Technology MDU-11 (above, manufactured by A & C Catalysts); Omicure 52 (above, manufactured by Chori GLEX Co., Ltd.).

Examples of commercially available PDMU products include, but are not limited to, Omicure 94 (all manufactured by Chori GLEX Co., Ltd.). Examples of commercially available TBDMU products include, but are not limited to, Omicure 24 (manufactured by Chori GLEX Co., Ltd.) and U-CAT 3512T (manufactured by Sun Appro Co., Ltd.). Examples of commercially available aliphatic dimethylurea products include, but are not limited to, U-CAT 3513N (manufactured by Sun Appro Co., Ltd.).

The content of ureas is preferably 1 part by mass or more and 15 parts by mass or less, and more preferably 2 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total epoxy resin contained in the curable resin composition of the present invention. When the content of ureas is 1 part by mass or more, the epoxy resin contained in the epoxy resin composition tends to be sufficiently cured and cured, and the mechanical properties and heat resistance can be improved. On the other hand, when the content of ureas is 15 parts by mass or less, the toughness of the cured resin product tends to be kept high.

The imidazoles used as the component (d1) may be imidazole, and imidazole adduct, inclusion imidazole, microcapsule type imidazole, imidazole compound coordinated with a stabilizer, and the like can also be used. They have a nitrogen atom with an unshared electron pair in their structure, which activates the epoxy groups of component (A) and component (B), and also activates other epoxy resins used in combination. It can be used to accelerate curing. Specific examples of the imidazole include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-phenyl imidazole, 2-phenyl-4. -Methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2- Undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazolium trimerite, 1-cyanoethyl-2-undecylimidazolium trimerite, 1-cyanoethyl-2- Phenylimidazolium trimellitate, 2,4-diamino-6- (2'-methylimidazolyl- (1'))-ethyl-s-triazine, 2,4-diamino-6- (2'-undecylimidazolyl-) (1'))-Ethyl-s-triazine, 2,4-diamino-6- (2'-ethyl-4-methylimidazolyl- (1'))-ethyl-s-triazine, 2,4-diamino-6 -(2'-Methylimidazolyl- (1'))-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 1-cyanoethyl-2 Examples of this include -phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and the like. It is not limited. The imidazole treated with adduct treatment, inclusion treatment with a different molecule, microcapsule treatment, or coordinated with a stabilizer is a modification of the above-mentioned imidazole. By reducing the activity of imidazole by adduct treatment, inclusion treatment with different molecules, microcapsule treatment, or by coordinating a stabilizer, it promotes hardening and hardening while exhibiting excellent pot life in the low temperature region. High ability.

Further, as the imidazoles, commercially available products may be used. Examples of commercially available imidazole products include 2E4MZ, 2P4MZ, 2PZ-CN, C11Z-CNS, C11Z-A, 2MZA-PW, 2MA-OK, 2P4MHZ-PW, 2PHZ-PW (all manufactured by Shikoku Chemicals Corporation). However, it is not limited to these. Commercially available products of imidazole adduct include, for example, PN-50, PN-50J, PN-40, PN-40J, PN-31, and PN-23, which have a structure in which an imidazole compound is ring-opened and added to an epoxy group of an epoxy resin. , PN-H (above, manufactured by Ajinomoto Fine-Techno Co., Ltd.) and the like, but are not limited thereto. Examples of commercially available products of subsumed imidazole include TIC-188, KM-188, HIPA-2P4MHZ, NIPA-2P4MHZ, TEP-2E4MZ, HIPA-2E4MZ, NIPA-2E4MZ (all manufactured by Nippon Soda Corporation). , Not limited to these. Commercially available products of microcapsule type imidazole include, for example, Novacure HX3721, HX3722, HX3742, HX3748 (above, manufactured by Asahi Kasei Corporation); LC-80 (above, manufactured by A & C Catalysts), but are limited thereto. It's not a thing. The imidazole compound coordinated with the stabilizer is, for example, a cure duct P-0505 (bisphenol A diglycidyl ether / 2-ethyl-4-methylimidazole adduct), which is an imidazole adduct manufactured by Shikoku Kasei Kogyo Co., Ltd. It can be prepared by combining L-07N (epoxy-phenol-borate ester compound), which is a stabilizer manufactured by Shikoku Kasei Kogyo Co., Ltd. Similar effects can be obtained by using imidazole compounds such as various imidazoles and imidazole adducts mentioned above instead of the cure duct P-0505. As the imidazole compound before coordinating the stabilizer, a compound having low solubility in an epoxy resin is preferably used, and from this point of view, Cure Duct P-0505 is preferable.

The content of imidazoles is preferably 1 part by mass or more and 15 parts by mass or less, and more preferably 2 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total epoxy resin contained in the curable resin composition of the present invention. When the content of imidazoles is 1 part by mass or more, the epoxy resin contained in the epoxy resin composition tends to have sufficient curing, curing promoting action, and heat resistance. On the other hand, when the content of imidazoles is 15 parts by mass or less, a cured resin product having better mechanical properties tends to be obtained.

Examples of the aromatic amines used as the component (d1) include 3,3'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-4,4'-diaminodiphenylmethane, and the like. 3,3'-diethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-di -T-butyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5 '-Diethyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraisopropyl -4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-5,5'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetra-t-butyl -4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylene diamine, diethyltoluenediamine, etc. However, the present invention is not limited to these. Among them, it is preferable to use 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone, which are excellent in heat resistance and elastic modulus and can obtain a cured product having a small decrease in heat resistance due to linear expansion coefficient and moisture absorption. .. 4,4'-diaminodiphenyl sulfone is also preferable in that the tack life of the prepreg can be maintained for a long period of time. Although 3,3'-diaminodiphenyl sulfone may be inferior to 4,4'-diaminodiphenyl sulfone in the tack life of the prepreg and the heat resistance of the cured product, it is preferable because it can increase the elastic modulus and toughness of the cured product. .. Further, it is preferable to mix 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone at the same time because it is easy to adjust the heat resistance and elastic modulus of the cured product. These aromatic amines may be used alone or in combination as appropriate. Regarding the blending amount of aromatic amines, especially in diaminodiphenyl sulfone, the active hydrogen equivalent number of the amino group is 0.5 to 1. the epoxy equivalent number of all the epoxy resins contained in the curable resin composition of the present invention. It is preferably 5 times, more preferably 0.6 to 1.4 times. By increasing the blending amount of these epoxy resin curing agents to 0.5 to 1.5 times, the elastic modulus, toughness, and heat resistance of the cured resin tend to be in a good range.

In addition, commercially available products may be used as the aromatic amines. Commercially available 4,4'-diaminodiphenyl sulfone products include Seika Cure S (active hydrogen equivalent 62 g / eq, manufactured by Wakayama Seika Kogyo Co., Ltd.) and SumiCure S (active hydrogen equivalent 62 g / eq, manufactured by Sumitomo Chemical Co., Ltd.). However, examples of commercially available 3,3'-diaminodiphenyl sulfone products include, but are not limited to, 3,3'-DAS (active hydrogen equivalent 62 g / eq, manufactured by Mitsui Kagaku Fine Co., Ltd.). Other commercially available aromatic amines include MDA-220 (active hydrogen equivalent 50 g / eq, manufactured by Mitsui Kagaku Co., Ltd.), "jER Cure (registered trademark)" W (active hydrogen equivalent 45 g / eq, Japan Epoxy). Resin Co., Ltd., Lonzacure (registered trademark) M-DEA (active hydrogen equivalent 78 g / eq), "Lonzacure (registered trademark)" M-DIPA (active hydrogen equivalent 92 g / eq), "Lonzacure (registered trademark)" Examples thereof include, but are not limited to, M-MIPA (active hydrogen equivalent 78 g / eq) and “Lonzacure®” DETDA 80 (active hydrogen equivalent 45 g / eq) (all manufactured by Lonza Co., Ltd.).

Examples of other amine-based curing agents that can be used as the component (d1) include meta-phenylenediamine, diaminodiphenylmethane, m-xylylenediamine, isophoronediamine, and triethylenetetramine. Examples of the acid anhydride that can be used as the component (d1) include hydrogenated methylnadic acid anhydride and methylhexahydrophthalic acid anhydride.

As the radical polymerization initiator that can be used as the component (d2), azo compounds, peroxide compounds, photoradical polymerization initiators and the like can be used, and the radical polymerization initiator is particularly selected from the peroxide compounds. It is preferable to use at least one curing agent.

Examples of azo compounds include 2,2-azobis (isobutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate), and the like. 2,2-Azobis (2-methylbutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), 2,2-azobis (N-butyl-2-methylpropionamide), dimethyl 1,1- Examples thereof include azobis (1-cyclohexanecarboxylate).

Examples of peroxide compounds include methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetone peroxide, 1,1-bis (t-butyl peroxy) 3,3,5-trimethylcyclohexane, and 1 , 1-bis (t-hexyl peroxy) cyclohexane, 1,1-bis (t-hexyl peroxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2, 2-Bis (4,5-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, n-butyl 4,4-bis (t-butylperoxy) valerate , 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butylhydroperoxide, P-menthanhydroperoxide, 1,1 , 3,3-Tetramethylbutylhydroperoxide, t-hexylhydroperoxide, 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) hexin-3, isobutyrylper Oxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, lauric acid peroxide, m-tolu oil peroxide, benzoyl peroxide, diisopropylperoxydicarbonate, bis (4-t) -Butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) ) Peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, α, α'-bis (neodecanoyl peroxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3 3,-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyne Odecanoate, 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-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , T-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, t-butylperoxy-3,5, 5-trimethylhexanoate, t-hexyl peroxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoyl) Peroxy) hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxy-m-toroil benzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, t -Butylperoxyallyl monocarbonate, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, dibenzoyl peroxide, di-t-hexyl peroxide, diisopropylbenzene hydroperoxide, etc. Be done.

Examples of the photoradical polymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, and 2-hydroxy-1- [4. -[4- (2-Hydroxy-2-methyl-propionyl) benzyl] phenyl] -2-methylpropan-1-one, t-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl -1-Phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexyl-phenylketone, benzoinmethyl ether, benzoinethyl ether, benzoinisopropyl ether, benzoinisobutyl ether, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate and the like can be mentioned.

The above compound can be used alone as the component (d2) or in combination of two or more, but in terms of storage stability of the prepreg, a compound having a 10-hour half-life temperature of 100 ° C. or higher is preferable. Used for. The amount of the component (d2) used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the total epoxy resin and all (meth) acrylate compounds contained in the curable resin composition of the present invention. , 0.2 to 3 parts by mass is more preferable. When the content of the component (d2) is 0.1 parts by mass or more, the (meth) acrylate compounds contained in the curable resin composition tend to be sufficiently cured. On the other hand, when the content of the component (d2) is 5 parts by mass or less, a resin composition having excellent storage stability tends to be obtained. The total (meth) acrylate compounds are the (meth) acrylate compounds as the component (C), or the component (G) when the curable resin composition of the present invention further contains the component (G) described later. It means the total of (meth) acrylate compounds as (C) and component (G).

<Ingredient (E)>
The component (E) is a compound having a polysiloxane structure. Polysiloxane refers to having a repeating unit of a siloxane bond, which is a bond between a silicon atom and an oxygen atom. By adding the component (E) to the matrix resin containing the component (A1) epoxy resin and the component (C) (meth) acrylate compounds, the resin film is not chipped or the resin is not removed, and a prepreg without impregnation spots is obtained. can get. A surface conditioner containing a compound having a polysiloxane structure may be used. The surface conditioner is an additive that adjusts surface tension, compatibility, polarity, and the like. The surface conditioner may contain a compound other than the compound having a polysiloxane structure, and examples of the other component include a solvent and a diluent. Specifically, the solvent includes toluene, xylene, isopropyl alcohol, and n. -Butanol, isobutanol, monophenyl glycol, white spirit, methoxypropyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, butyrolactone, metaxylene hexafluorolide, etc. can be used, and alkyl monoglycidyl as a diluent can be used. Ether, alkylphenol monoglycidyl ether, 1,6-hexanediol diglycidyl ether, polyglycol diglycidyl ether, diglycidyl aniline, diglycidyl-o-toluidine and the like can be used.

In this resin composition, with respect to 100 parts by mass of all the components other than the component (E) of the curable resin composition, the content of the component (E) is such that a resin film having no resin chipping or resin removal is obtained. The amount is preferably 0.05 parts by mass or more, more preferably 0.07 parts by mass or more, and 0.08 parts by mass or more, because a prepreg without impregnation spots can be obtained. Is even more preferable. Since the elastic modulus and elongation can be appropriately maintained in the bending test of the cured resin product, it is preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less, and 0.2 parts by mass or less. The following is more preferable. Further, with respect to 100 parts by mass of the component (C), the component (E) can obtain a resin film without resin chipping or resin removal, and a prepreg without impregnation spots can be obtained. Therefore, 0.08. It is preferably parts by mass or more, and more preferably 0.1 parts by mass or more. Since the elastic modulus and elongation can be appropriately maintained in the bending test of the cured resin product, it is preferably 5 parts by mass or less, and more preferably 2 parts by mass or less.

Examples of the compound having a polysiloxane structure include dimethyl silicone oil, alkyl-modified silicone oil, amino-modified silicone oil, carboxyl-modified silicone oil, epoxy-modified silicone oil, fluorine-modified silicone oil, alcohol-modified silicone oil, and polyether-modified silicone oil. , Methylphenyl silicone oil, methylhydrogen silicone oil, mercapto-modified silicone oil, higher fatty acid-modified silicone oil, phenol-modified silicone oil, methacrylic acid-modified silicone oil, polyether-modified silicone oil, methylstyryl-modified silicone oil and the like can be used. Polyether-modified silicone oil is preferable because resin chipping is unlikely to occur. As the polysiloxane, modified polysiloxane can be used, and examples thereof include polyether modification, polyester modification, fatty acid ester modification, polyol modification, acrylic resin modification, phenyl modification, fluorine modification, and aralkyl modification. Among these, polyether-modified polysiloxane is preferable because resin chipping of the resin film is unlikely to occur.

It is more preferable to add a polyether structure to the side chain of the polysiloxane structure because compatibility, surface tension, and polarization can be easily adjusted. More preferably, by adding a polyether structure having ethylene oxide (EO) and / or propylene oxide (PO) to the side chain of the polysiloxane structure, hydrophilicity can be imparted to EO and hydrophobicity can be imparted to PO. The polarity of the compound having a polysiloxane structure can be adjusted. As these compounds having a polysiloxane structure, one type may be used alone, or two or more types may be used in combination.

As the component (E), a commercially available product may be used. As a commercially available surface conditioner (component (E)) containing a compound having a polysiloxane structure or a compound having a polysiloxane structure, for example, a compound having a polyether-modified polysiloxane structure may be used. , BYK-300 (dimethylsiloxane xylene / isobutanol), BYK-302 (dimethylsiloxane), BYK-306 (dimethylsiloxane xylene / monophenylglycol), BYK-307 (polydimethylsiloxane), BYK- 320 (polymethylalkylsiloxane white spirit / methoxypropyl acetate), BYK-325 and BYK-325N (polyester-modified polymethylalkylsiloxane PMA / monophenylglycol), BYK-326 (polymethylalkylsiloxane), BYK-330 (poly) Ether-modified polydimethylsiloxane methoxypropyl acetate), BYK-331 (polydimethylsiloxane), BYK-333 (polydimethylsiloxane), BYK-342 (polydimethylsiloxane dipropylene glycol monomethyl ether), BYK-345 (siloxane), BYK -346 (siloxane dipropylene glycol monomethylether), BYK-347 (siloxane), BYK-348 (siloxane), BYK-349 (siloxane), BYK-375 (polyether with hydroxyl group-polydimethylsiloxane dipropylene modified with polyester) Glycol monomethyl ether), BYK-377 (hydroxyl-containing polyether-modified polydimethylsiloxane), BYK-378 (polydimethylsiloxane), BYK-3455 (polydimethylsiloxane), BYK-3760 (polydimethylsiloxane), and Shin-Etsu Chemical Industry Co., Ltd. KP-124, KP-109, KP-110, KP-121, KP-118, KP-341, KP-112, KP-125, KP-101, KP-106, KP-120, etc. manufactured by KP-124 Co., Ltd. (The main component and solvent are shown in parentheses). Compounds having a polyester-modified polysiloxane structure include BYK-310, BYK-313, BYK-315N, and BYK-370 manufactured by Big Chemie Co., Ltd., and compounds having a fatty acid ester-modified polysiloxane structure include KP. -626 etc. (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), as compounds having a polyol-modified polysiloxane structure, KP-105, KP-104, etc. (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Compounds having an acrylic resin-modified polysiloxane structure include KP-611 and the like (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), and compounds having a phenyl-modified polysiloxane structure include KP-327 and KP-323. , KP-322, etc. (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), as a compound having a fluorine-modified polysiloxane structure, KP-625, etc. (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), aralkyl-modified Examples of the compound having a polysiloxane structure include BYK-322, BYK-323, etc. (all trade names, manufactured by Big Chemie Co., Ltd.), KP-623, KP-624, KP-620, etc. (all trade names, trade names, etc.). (Manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like.

<Ingredient (F)>
The purpose of this resin composition is to improve the workability by adjusting the viscoelasticity of the present resin composition when it is not cured as the component (F), and to improve the strength, elastic modulus, toughness, and heat resistance of the cured resin composition. Then, the epoxy resin described below may be contained. The component (F) is not particularly limited as long as it is an epoxy resin other than the bisphenol type epoxy resin used as the component (A) or the component (B) and is suitable for the above purpose, but is a bifunctional or higher functional epoxy resin. Is preferably used. For example, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol Z type epoxy resin, bisphenol AD type epoxy resin, etc., bisphenol type epoxy resin other than those used as component (A) and component (B), biphenyl type epoxy resin, Naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, tetraglycidyl diaminodiphenyl methane, glycidyl amine type epoxy resin such as triglycidyl aminophenol; Examples thereof include glycidyl ether type epoxy resins other than the above such as (glycidyloxyphenyl) ethane and tris (glycidyloxy) methane, modified epoxy resins thereof, and phenol aralkyl type epoxy resins. Since trifunctional or higher functional epoxy resins can obtain better strength, elasticity, and heat resistance, para-type and meta-type triglycidyl aminophenol type epoxy resins, tetraglycidyl diaminodiphenylmethane type epoxy resins, and phenol novolac type epoxys can be obtained. Resins and cresol novolac type epoxy resins are preferably used.

Commercially available products of the epoxy resin used as the component (F) include, for example, jER1001 (epoxy equivalent 475 g / eq), jER1002 (epoxy equivalent 650 g / eq), jER604 (epoxy equivalent 120 g / eq), jER630 (epoxy equivalent 98 g / eq). eq), jER1032H60 (epoxy equivalent 169g / eq), jER152 (epoxy equivalent 175g / eq), jER154 (epoxy equivalent 178g / eq), YX-7700 (epoxy equivalent 273g / eq), YX-4000 (epoxy equivalent 186g / eq) (Above, manufactured by Mitsubishi Chemical Co., Ltd.); GAN (epoxy equivalent 125 g / eq), GOT (epoxy equivalent 135 g / eq), NC-2000 (epoxy equivalent 241 g / eq), NC-3000 (epoxy equivalent 275 g / eq) (The above is manufactured by Nippon Kayaku Co., Ltd.); YDPN-638 (epoxy equivalent 180 g / eq), TX-0911 (epoxy equivalent 172 g / eq) (above, manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), Epon165 (epoxy equivalent 230 g / eq) (Above, manufactured by Momentive Specialty Chemicals); MY-0500 (epoxy equivalent 110 g / eq), MY-0600 (epoxy equivalent 106 g / eq), ECN-1299 (epoxy equivalent 230 g / eq) (above, Huntsman Japan Co., Ltd.) (Manufactured by); HP-4032 (epoxy equivalent 150 g / eq), HP-4700 (epoxy equivalent 162 g / eq), HP-7200 (epoxy equivalent 265 g / eq), TSR-400 (all manufactured by DIC Co., Ltd.); AER4152, AER4151, LSA3301, LSA2102 (above, manufactured by Asahi Kasei Co., Ltd.), ACR1348 (epoxy equivalent 350 g / eq) (above, manufactured by ADEKA Co., Ltd.); DER852 (epoxy equivalent 320 g / eq), DER858 (epoxy equivalent 400 g / eq) ( As mentioned above, (manufactured by THE DOWN CHEMICAL COMPANY) and the like can be mentioned, but the present invention is not limited thereto.

The content of the component (F) is preferably 5 to 35 parts by mass, more preferably 10 to 30 parts by mass, out of 100 parts by mass of the total epoxy resin contained in the curable resin composition of the present invention. When the content of the component (F) is 5 parts by mass or more, the effect of improving the physical properties tends to be exhibited satisfactorily, which is preferable. On the other hand, when the content of the component (F) is 35 parts by mass or less, the characteristics of the curable resin composition of the present invention tend to be kept good, which is preferable.

<Ingredient (G)>
The present resin composition contains the following monofunctional (meth) acrylates as the component (G) for the purpose of controlling the crosslinked structure of the present resin composition, lowering the viscosity, and imparting adhesion. It may contain compounds. Here, the "monofunctional (meth) acrylate compound" means an acrylate compound and / or a methacrylate compound having one double bond in one molecule. Specific examples of the compound that can be used as the component (G) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and tetrahydrofurfuryl (meth). ) Acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, 2- (meth) acryloyloxymethyl-2-methylbicycloheptane, adamantyl (meth) acrylate, benzyl (Meta) acrylate, phenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-methoxyethyl (Meta) acrylate, 3-methoxybutyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, 4-acryloyloxymethyl-2-methyl-2 -Ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, o-phenylphenol (meth) acrylate, ethoxylated o-phenylphenol (meth) acrylate, N -(Meta) acrylic acid esters such as acryloyloxyethyl hexahydrophthalimide, paracumylphenol (meth) acrylate, ethoxylated paracumylphenol (meth) acrylate, trimethylpropanformal (meth) acrylate; vinyl acetate, Vinyl ester monomers such as vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenylvinyl ether; acrylamide, N, Acrylamides such as N-dimethylacrylamide, N, N-dimethylmethacrylicamide, N-methylolacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, Nt-butylacrylamide, acryloylmorpholine, hydroxyethylacrylamide, methylenebisacrylamide, etc. Kind and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, a compound having a cyclic structure in the molecule is preferable because the obtained composition has a low curing shrinkage rate and the obtained cured product has excellent strength.

In the present invention, the content of the component (G) is not particularly limited, but is preferably in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the total epoxy resin contained in the present resin composition. When the content of the component (G) is 0.1 parts by mass, the effect of improving the physical properties tends to be exhibited satisfactorily, which is preferable. On the other hand, when the content of the component (G) is 5 parts by mass, the characteristics of the curable resin composition of the present invention tend to be kept good, which is preferable.

<Ingredient (H)>
The component (H) is an oxazolidone type epoxy resin. The oxazolidone type epoxy resin is an epoxy resin having an oxazolidone cyclic structure, which improves the workability of a prepreg containing the epoxy resin composition at room temperature, and also improves the elasticity and heat resistance of the cured product of the epoxy resin composition. Improves sex and adhesion to reinforcing fibers.

The oxazolidone cyclic structure is formed by the addition reaction of an isocyanate group and an epoxy group. The method for producing the oxazolidone skeleton-containing epoxy resin in the present invention is not particularly limited, and for example, by reacting an isocyanate compound and an epoxy resin having a biphenyl skeleton in the presence of an oxazolidone ring-forming catalyst, the amount is substantially theoretical. Obtainable. The isocyanate compound and the epoxy resin are preferably reacted in an equivalent ratio of 1: 2 to 1:10, and when the ratio of both is in the above range, the heat resistance and water resistance of the cured epoxy resin product become better. There is a tendency. In the present invention, various isocyanate compounds can be used as raw materials, but in order to incorporate the oxazolidone cyclic structure into the skeleton of the epoxy resin, an isocyanate compound having a plurality of isocyanate groups is preferable. Further, in order for the cured product of the epoxy resin composition containing the component (H) to have high heat resistance, diisocyanate having a rigid structure is preferable.

Specific examples of the isocyanate compound used as a raw material include, for example, methanediisocyanate, butane-1,1-diisocyanate, ethane-1,2-diisocyanate, butane-1,2-diisocyanate, transvinylene diisocyanate, and propane-1,3-. Diisocyanate, butane-1,4-diisocyanate, 2-butene-1,4-diisocyanate, 2-methylbutene-1,4-diisocyanate, 2-methylbutane-1,4-diisocyanate, pentane-1,5-diisocyanate, 2, 2-Dimethylpentane-1,5-diisocyanate, hexane-1,6-diisocyanate, heptane-1,7-diisocyanate, octane-1,8-diisocyanate, nonane-1,9-diisocyanate, decane-1,10-diisocyanate , Didimethylsilane diisocyanate, diphenylsilane diisocyanate, ω, ω'-1,3-dimethylbenzenediisocyanate, ω, ω'-1,4-dimethylbenzenediisocyanate, ω, ω'-1,3-dimethylcyclohexanediisocyanate, ω, ω'-1,4-dimethylcyclohexanediisocyanate, ω, ω'-1,4-dimethylnaphthalenediocyanate, ω, ω'-1,5-dimethylnaphthalenediocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4 -Diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, 1-methylbenzene-2, 4-Diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-3,5-diisocyanate, diphenyl ether-4,4'-diisocyanate, diphenyl ether-2, 4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,3'- Dimethoxybisphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'- Bifunctional isocyanate compounds such as dimethoxydiphenylmethane-3,3'-diisocyanate, norbornene diisocyanate, diphenylsulfite-4,4'-diisocyanate, diphenylsulphon-4,4'-diisocyanate; polymethylenepolyphenylisocyanate, triphenylmethanetri Polyfunctional isocyanate compounds such as isocyanate, tris (4-phenylisocyanate thiophosphate) -3,3', 4,4'-diphenylmethanetetraisocyanate; multimers such as dimer and trimer of the isocyanate compound, alcohol and Examples thereof include, but are not limited to, blocked isocyanates and bisurethane compounds masked with phenol. Two or more of these isocyanate compounds may be used in combination.

Among the above-mentioned isocyanate compounds, since the heat resistance tends to be improved, it is preferably a bifunctional or trifunctional isocyanate compound, more preferably a bifunctional isocyanate compound, and further preferably isophorone, benzene, toluene, diphenylmethane, naphthalene, norbornenepoly. It is a bifunctional isocyanate compound having a skeleton selected from methylenepolyphenylene polyphenyl and hexamethylene. If the number of functional groups of the isocyanate compound is too large, the storage stability of the epoxy resin composition tends to decrease, and if it is too small, the heat resistance of the cured product of the epoxy resin composition tends to decrease.

Further, various epoxy resins can be used as the epoxy resin as the raw material of the component (H), but in order to efficiently incorporate the oxazolidone cyclic structure into the skeleton of the epoxy resin, epoxy groups are formed at both ends of the molecule. Epoxy resin having is preferable. Specific examples of the epoxy resin used as the raw material of the component (H) include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, and the like. Epoxy resins derived from divalent phenols such as tetrabromobisphenol A; 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1- (4-hydroxyphenyl) ethane, 4,4- [1 -[4- [1- (4-Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] Epoxy resin derived from tris (glycidyloxyphenyl) alkanes such as bisphenol; phenol novolac, cresol novolac, bisphenol A novolac Examples thereof include epoxy resins derived from Novolak such as, but the present invention is not particularly limited thereto. As the epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin and the like are particularly preferable because the viscosity of the component (H) is not too high.

As the isocyanate compound, a bifunctional isocyanate having a toluene skeleton such as tolylene diisocyanate (for example, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene-2,5-diisocyanate, 1-methylbenzene-2,6) -Diisocyanate, 1-methylbenzene-3,5-diisocyanate) 1 molecule and 2 molecules of bisphenol A diglycidyl ether as an epoxy resin are mixed and reacted to obtain an addition reaction product that has the workability of prepreg at room temperature. It is particularly preferable to improve the heat resistance of the cured product of the epoxy resin composition.

Epoxy resins (component (H)) having an oxazolidone cyclic structure that can be obtained as commercially available products include AER4152, AER4151, LSA3301, LSA2102 (trade name, manufactured by Asahi Kasei E-Materials Co., Ltd.) and ACR1348 (trade name, stock). ADEKA), DER852, DER858 (trade name, THE DOWN CHEMICAL COMPANY), TSR-400 (trade name, DIC), etc., all of which are preferably used in the present invention, such as AER4152 and TSR. -400 is particularly preferable. As the component (H), two or more kinds of epoxy resins as described above may be used in combination.

The content of the component (H) is preferably 5 parts by mass or more and 60 parts by mass or less out of 100 parts by mass of the total epoxy resin contained in the epoxy resin composition of the present invention. When the content of the component (H) is 5 parts by mass or more, a cured resin product having excellent heat resistance and mechanical properties tends to be obtained. It is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 30 parts by mass or more. On the other hand, when the content of the component (H) is 60 parts by mass or less, a prepreg having excellent tack and drape properties can be obtained, and a cured resin product having high fracture toughness and no voids tends to be obtained. is there. It is more preferably 58 parts by mass or less, and further preferably 55 parts by mass or less. The content of the component (H) is more preferably in the range of 10 to 58 parts by mass, further preferably in the range of 15 to 55 parts by mass, and particularly preferably in the range of 30 to 55 parts by mass. .. In the present invention, the amounts (parts by mass) of the components (A), (B), (F), and (H) are also mass% with respect to the total mass of the total epoxy resin contained in the epoxy resin composition of the present invention. It can be interpreted.

<Ingredient (I)>
The thermosetting resin is used as a component (I) in the curable resin composition of the present invention, if necessary, for the purpose of controlling the resin flow during molding of the curable resin composition of the present invention and imparting toughness to the cured resin product. Can be blended. That is, it is preferable that the present resin composition further contains a thermoplastic resin as the component (I).

The present resin composition preferably contains the component (I) by 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the present resin composition, and contains 2 parts by mass or more and 10 parts by mass or less. Is more preferable. When the content of the component (I) is 1 part by mass or more, the resin flow control and the effect of improving the physical properties tend to be satisfactorily exhibited, which is preferable. On the other hand, when the content of the component (I) is 15 parts by mass or less, the viscosity of the curable resin composition, the heat resistance and mechanical properties of the cured resin, and the tack and drape properties of the prepreg tend to be well maintained. It is preferable because it is located in.

Examples of the thermoplastic resin include polyamide, polyester, polycarbonate, polyether sulfone, polyphenylene ether, polyphenylene sulfide, polyether ether ketone, polyether ketone, polyimide, polytetrafluoroethylene, polyether, polyolefin, liquid crystal polymer, polyarylate, and the like. Polysulphon, polyacrylonitrile styrene, polystyrene, polyacrylonitrile, polymethylmethacrylate, ABS (acrylonitrile, butadiene, styrene copolymer), AES (acrylonitrile, ethylene propylene rubber, styrene copolymer), ASA (acrylonitrile, acrylic rubber, styrene) Copolymers), polyvinyl chloride, polyvinyl formal resin, phenoxy resin, block polymer and the like, but are not limited thereto. Among these, phenoxy resin, polyether sulfone, and polyvinyl formal resin are preferable because they are excellent in resin flow controllability and the like. Further, phenoxy resin and polyether sulfone are preferable from the viewpoint of further enhancing the heat resistance and flame retardancy of the cured resin product, and polyvinyl formal resin is suitable for tacking the obtained prepreg without impairing the heat resistance of the cured product. It is preferable from the viewpoint that the range can be easily controlled and the adhesiveness between the reinforcing fiber and the epoxy resin composition is improved. Block polymers are preferred because they improve toughness and impact resistance. One of these thermoplastic resins may be used alone, or two or more thereof may be used in combination.

Examples of the phenoxy resin include, but are not limited to, YP-50, YP-50S, YP70, ZX-1356-2, FX-316 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and the like. Examples of the polyvinyl formal resin include Vinilek (registered trademark) K (mass average molecular weight: 59,000), Vinilek L (mass average molecular weight: 66,000), Vinilek H (mass average molecular weight: 73,000), and Vinilek E (mass). Average molecular weight: 126,000) (above, manufactured by JNC Corporation) and the like, but are not limited thereto.

Further, when the cured resin product is required to have heat resistance exceeding 180 ° C., a polyether sulfone or a polyetherimide is preferably used. Specifically, as the polyether sulfone, Sumika Excel (registered trademark) 3600P (mass average molecular weight: 16,400), Sumika Excel 5003P (mass average molecular weight: 30,000), Sumika Excel 5200P (mass average molecular weight: 35, 000), Sumika Excel 7600P (mass average molecular weight: 45,300) (all manufactured by Sumitomo Chemical Co., Ltd.) and the like. Examples of the polyetherimide include ULTEM1000 (mass average molecular weight: 32,000), ULTEM1010 (mass average molecular weight: 32,000), ULTEM1040 (mass average molecular weight: 20,000) (all manufactured by SABIC Innovative Plastics Co., Ltd.) and the like. However, it is not limited to these.

Block copolymers include Nanostrength M52, Nanostrength M52N, Nanostrength M22, Nanostrength M22N, Nanostrength 123, Nanostrength 250, Nanostrength 250, Nanostrength 012, Nanostrength 012, Nanostrength , TPAE-23, TPAE-31, TPAE-38, TPAE-63, TPAE-100, PA-260 (all manufactured by T & K TOKA) and the like, but are not limited thereto.

<Arbitrary ingredient>
If necessary, the resin composition may contain various known additives as long as the effects of the present invention are not impaired, and the storage stability of the composition may be improved, or the cured product layer may be discolored or deteriorated. Antioxidants and light stabilizers can also be added to avoid this. Specific examples of this include, for example, various commercially available Sumitomo Chemical Co., Ltd. Sumilyzer BHT, Sumilyzer S, Sumilyzer BP-76, Sumilyzer MDP-S, Sumilyzer GM, Sumilyzer BBM-S, Sumilyzer WX-R, and Sumilyzer. NW, Sumilyzer BP-179, Sumilyzer BP-101, Sumilyzer GA-80, Sumilyzer TNP, Sumilyzer TPP-R, Sumilyzer P-16; Adekastab AO-20, Adekastab AO-30, Adekastab AO- 40, Adekastab AO-50, Adekastab AO-60AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 329K, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010; 292; Funkrill FA-711M, FA-712HM, etc. manufactured by Hitachi Kasei Kogyo Co., Ltd. can be mentioned.

The amount of these antioxidants and light stabilizers added is not particularly limited, but they should be added in the range of 0.001 to 5 parts by mass with respect to the total number of parts of the total epoxy resin and all (meth) acrylate compounds, respectively. Is preferable, and the range of 0.01 to 3 parts by mass is more preferable. Other additives include elastomers, thermoplastic elastomers, flame retardants (for example, phosphorus-containing epoxy resins, red phosphorus, phosphazene compounds, phosphates, phosphate esters, etc.), wetting dispersants, defoaming agents, defoaming agents, etc. Natural waxes, synthetic waxes, metal salts of linear fatty acids, acid amides, esters, mold release agents such as paraffins, crystalline silica, molten silica, calcium silicate, alumina, calcium carbonate, talc, barium sulfate, etc. Powders and metal oxides, metal hydroxides, glass fibers, carbon nanotubes, inorganic fillers such as fullerene, organic fillers such as carbon fibers and cellulose nanofibers, inorganic fillers with surface organic treatment, carbon black, red iron oxide, etc. Examples thereof include known additives such as colorants, silane coupling agents, and conductive materials. Further, if necessary, a slip agent, a polymerization inhibitor such as hydroquinone monomethyl ether, an ultraviolet absorber, or the like can be added. These may be used individually by 1 type, and may be used in combination of 2 or more type.

<Viscosity of curable resin composition>
The viscosity of the present resin composition at 60 ° C. is preferably 70 Pa · s or more, preferably 70 Pa · s or more, from the viewpoint of morphological retention of the obtained resin film, workability at the time of manufacturing the resin film, and impregnation property of the prepreg. -S or more is more preferable, and 80 Pa · s or more is further preferable. The upper limit of the viscosity is preferably 300 Pa · s or less, more preferably 270 Pa · s or less, and further preferably 250 Pa · s or less.

The minimum viscosity of the present resin composition is preferably 0.05 Pa · s, preferably 0.07 Pa · s, from the viewpoint of controlling the fluidity of the resin during molding (suppressing the disturbance of the reinforcing fibers). It is more preferably s, and even more preferably 0.1 Pa · s. The upper limit of the minimum viscosity is preferably 50 Pa · s, more preferably 40 Pa · s, and even more preferably 30 Pa · s. The minimum viscosity is defined as the point where the viscosity is the lowest in the viscosity curve obtained when the viscosity of the curable resin composition is measured in the temperature rising mode. The viscosity of the curable resin composition is, for example, a plate gap of 500 μm and a heating rate of 2 ° C./min using a 25 mmφ parallel plate with a rotational viscometer (“MARS 40” manufactured by Thermo Fisher Scientific Co., Ltd.). It is obtained by measuring at a temperature rise, an angular velocity of 10 rad / sec, and a stress of 300 Pa.

<Physical characteristics of resin plate>
The curable resin composition of the present invention preferably has a flexural modulus of the cured resin in the range of 3.5 to 6 GPa, and the elongation at break of the cured resin in the range of 6 to 15%. It is preferable to have. More preferably, the flexural modulus is 3.6 to 5 GPa and the elongation at break is 7 to 14%. If the elastic modulus is less than 3.5 GPa or the elongation at break is well over 15%, the static strength of the fiber-reinforced composite material may be insufficient. If the flexural modulus exceeds 6 GPa or the elongation at break is less than 6%, the toughness of the fiber-reinforced composite material tends to be insufficient, and the impact resistance of the fiber-reinforced composite material may be insufficient. is there.

<Manufacturing method and application of curable resin composition>
The curable resin composition of the present invention is not limited to this, but can be obtained, for example, by mixing the above-mentioned components. Examples of the mixing method of each component include a method using a mixer such as a three-roll mill, a planetary mixer, a kneader, a homogenizer, and a homodisper. This resin composition can be used for producing a prepreg by impregnating a reinforcing fiber aggregate, for example, as described later. In addition, a film of the present resin composition can be obtained by applying the present resin composition to a paper pattern or the like and curing the present resin composition.

<Effect>
The present resin composition described above includes the above-mentioned component (A), component (B), component (C), component (D) and component (E), and if necessary, component (H) and component (I). Since the component (F), the component (G) and other additives are contained, a fiber-reinforced composite material having no poor appearance and excellent mechanical properties can be obtained by using this resin composition.

〔Molding〕
The molded product of the present invention is formed from the cured product of the curable resin composition of the present invention described above. Examples of the molding method of the curable resin composition include an injection molding method (including insert molding of a film or a glass plate), an injection compression molding method, an extrusion method, a blow molding method, a vacuum molding method, a pressure molding method, and a calendar molding. Examples include a method and an inflation molding method. Among these, the injection molding method and the injection compression molding method are preferable, but are not limited to these, because they are excellent in mass productivity and can obtain a molded product with high dimensional accuracy. Since the molded product of the present invention is formed by molding the curable resin composition of the present invention, it has excellent mechanical properties. Therefore, it is applied to, for example, vehicle products, housings for mobile devices, furniture products, building material products, and the like. it can.

<Film made of curable resin composition>
One of the embodiments of the molded product of the present invention is its use as a film. This film is useful as an intermediate material for producing a prepreg, and also as a surface protective film or an adhesive film by being attached to a substrate and then cured. The method of use thereof is not limited to this, but it is preferable to apply the curable resin composition of the present invention to the surface of a base material such as a paper pattern. The obtained coating layer may be used as a film by sticking it to another base material in an uncured state and curing it, or may be used as a film by curing the coating layer itself.

[Prepreg]
The prepreg of the present invention is obtained by impregnating the reinforcing fiber aggregate with the curable resin composition of the present invention described above. As a method for impregnating the reinforcing fiber aggregate with the present resin composition, a known method may be used. For example, a wet method in which the present resin composition is dissolved in a solvent such as methyl ethyl ketone or methanol to reduce the viscosity and then impregnated. , Hot melt method (dry method), etc., in which the viscosity is reduced by heating and then impregnated, but the method is not limited thereto.

The wet method is a method in which the reinforcing fibers are immersed in a solution of the curable resin composition, pulled up, and the solvent is evaporated using an oven or the like. On the other hand, in the hot melt method, a method of directly impregnating the reinforcing fibers with a curable resin composition whose viscosity has been reduced by heating and a film in which the curable resin composition is once coated on a release paper or the like are prepared. Then, there is a method in which the film is laminated from both sides or one side of the reinforcing fiber and the reinforcing fiber is impregnated with the resin by heating and pressurizing. According to the hot melt method, there is virtually no solvent remaining in the prepreg, which is preferable.

The content of the curable resin composition of the prepreg of the present invention (hereinafter referred to as "resin content") is preferably 15 to 50% by mass, assuming that the total mass of the prepreg of the present invention is 100%. It is more preferably 20 to 45% by mass, further preferably 25 to 40% by mass. When the resin content is 15% by mass or more, the adhesiveness between the reinforcing fiber aggregate and the curable resin composition can be sufficiently ensured, and when it is 50% by mass or less, the mechanical properties can be maintained high.

The reinforcing fibers constituting the reinforcing fiber aggregate are not particularly limited, and the reinforcing fibers known as the reinforcing fibers constituting the fiber-reinforced composite material may be appropriately selected depending on the application and the like. As a specific example, various inorganic fibers or organic fibers such as carbon fiber, aramid fiber, nylon fiber, high-strength polyester fiber, glass fiber, boron fiber, alumina fiber and silicon nitride fiber can be used. Among these, carbon fiber, aramid fiber, glass fiber, boron fiber, alumina fiber and silicon nitride fiber are preferable from the viewpoint of specific strength and specific elasticity, and carbon fiber is particularly preferable from the viewpoint of mechanical properties and weight reduction. When carbon fiber is used as the reinforcing fiber, the surface treatment with metal may be applied. These reinforcing fibers may be used alone or in combination of two or more.

From the viewpoint of the rigidity of the fiber-reinforced composite material obtained by curing the prepreg of the present invention, the strand tensile strength of the carbon fiber is preferably 1 to 9 GPa, more preferably 1.5 to 9 GPa, and the strand tensile modulus of the carbon fiber. Is preferably 150 to 1,000 GPa, more preferably 200 to 1,000 GPa. The strand tensile strength and the strand tensile modulus of the carbon fiber are values measured in accordance with JIS R7601: 1986.

The form of the reinforcing fiber aggregate is not particularly limited, and a form used as a base material of a normal prepreg can be adopted. For example, even if the reinforcing fibers are aligned in one direction (UD: UniDirection). It may be a woven fabric, a non-woven fabric, or a non-crimp fabric. Since the prepreg of the present invention is obtained by impregnating the reinforcing fiber aggregate with the epoxy resin composition of the present invention, it can be used as a raw material for fiber reinforced plastic having excellent mechanical properties.

[Fiber reinforced plastic]
The fiber-reinforced plastic of the present invention comprises the cured product of the curable resin composition of the present invention described above and the reinforcing fiber. The fiber-reinforced plastic of the present invention is not limited to this, but can be obtained by molding, for example, by laminating the above-mentioned prepreg of the present invention and then heating and curing the curable resin while applying pressure to the laminate. Be done. Since the fiber-reinforced plastic of the present invention is excellent in mechanical properties, flame retardancy, heat resistance, electromagnetic wave shielding property and the like, it is preferable to contain carbon fiber as the reinforcing fiber.

Examples of the method for molding the fiber-reinforced plastic of the present invention include a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, a sheet wrap molding method, and a curable resin composition for filaments and preforms of reinforcing fibers. Examples thereof include RTM (Resin Transfer Molding), VaRTM (Vacum assist Resin Transfer Molding: vacuum resin impregnation manufacturing method), filament winding, RFI (Resin Film Information), etc., in which an object is impregnated and cured to obtain a molded product. It is not limited to the method.

The wrapping tape method is a method of winding a prepreg around a core metal such as a mandrel to form a tubular body made of fiber reinforced plastic, and is preferably used when producing a rod-shaped body such as a golf shaft or a fishing rod. More specifically, the prepreg is wound around the mandrel, a wrapping tape made of a thermoplastic film is wound on the outside of the prepreg to fix the prepreg, and the resin is heat-cured in an oven, and then the core metal is used. It is a method of obtaining a fiber-reinforced plastic tubular body by extracting. Further, in the internal pressure molding method, a preform in which a prepreg is wound around an internal pressure applying body such as a tube made of a thermoplastic resin is set in a mold, and then a high pressure gas is introduced into the internal pressure applying body to apply pressure. At the same time, the mold is heated and molded. This method is preferably used when molding a complicated shape such as a golf shaft, a bat, a racket such as tennis or badminton.

The fiber reinforced plastic using the cured product of the curable resin composition of the present invention as a matrix resin is suitably used for sports applications, general industrial applications, and aerospace applications. More specifically, in sports applications, it is suitably used for golf shafts, fishing rods, rackets for tennis and badminton, stick applications such as hockey, and ski pole applications. Furthermore, in general industrial applications, structural materials for moving objects such as automobiles, ships, and railroad vehicles, drive shafts, leaf springs, wind turbine blades, pressure vessels, flywheels, paper rollers, roofing materials, cables, repair reinforcement materials, etc. Suitable for use.

<Structure>
The structure can be obtained from the fiber reinforced plastic of the present invention described above. This structure may consist only of the fiber reinforced plastic of the present invention, or may be composed of the fiber reinforced plastic of the present invention and other materials (for example, metal, injection-molded thermoplastic resin member, etc.). It may be what is done.

Since this structure is partially or wholly composed of the fiber reinforced plastic of the present invention, it is excellent in flame retardancy and heat resistance. This structure can also be applied to, for example, interior members of aircraft and automobiles, housings for electric / electronic devices, and the like.

[Fiber reinforced plastic tubular body]
The fiber-reinforced plastic tubular body is a tubular fiber-reinforced plastic, and is obtained by laminating, curing, and molding the above-mentioned prepreg by a known molding method such as a wrapping tape method. Since the fiber-reinforced plastic tubular body using the cured product of the cured composition has excellent breaking strength and elastic modulus, it can be suitably used for golf shafts, fishing rods and the like. The fiber-reinforced plastic tubular body can be obtained from a unidirectional prepreg in which reinforcing fibers aligned in one direction are impregnated with the resin composition of the present invention. Stack 2 prepregs so that the fiber direction of the unidirectional prepreg is -45 ° and + 45 ° with respect to the cylindrical axis direction, and further unidirectional prepreg so that the fiber direction is parallel to the cylindrical axis direction. A tubular body made of a composite material having an inner diameter of 6 mm can be produced by laminating 1 ply of a prepreg. Here, the mandrel is a round bar made of stainless steel.

Specifically, for example, it can be produced by the methods described in the following [1a] to [5a], but the present invention is not limited to this.
[1a] From the produced unidirectional prepreg, two rectangular prepregs having a length of 200 mm and a width of 76 mm are cut out so that the fiber axis direction is 45 degrees with respect to the long side direction. The fibers of these two prepregs are laminated so as to intersect each other and shifted by 9 mm in the short side direction.
[2a] The prepreg bonded to the release-processed mandrel is wound so that its long side and the mandrel axial direction are in the same direction.
[3a] A rectangular prepreg having a length of 200 mm and a width of 161 mm is cut out from the produced unidirectional prepreg so that the long side direction is the fiber direction, and the fiber direction is the same as the mandrel axis direction. Turn it around the mandrel so that it becomes.
[4a] Further, a heat-resistant film tape is wrapped around the tape as a wrapping tape to cover the wound material, and heat-molded in a curing furnace at 130 ° C. for 90 minutes. The width of the wrapping tape is 15 mm, the tension is 3N, the winding pitch (the amount of deviation at the time of winding) is 1 mm, and this is wrapped so as to have the same thickness as the laminated body.
[5a] After that, the mandrel is pulled out and the wrapping tape is removed to obtain a fiber-reinforced plastic tubular body.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. The raw materials used in Examples and Comparative Examples are shown below. The softening point and epoxy equivalent were measured under the following conditions.
1) Softening point: A value measured in accordance with JIS-K7234: 2008 (ring and sphere method). 2) Epoxy equivalent: A value measured in accordance with JIS-K7236: 2001.

"material"
<Ingredient (A)>
jER4007P: Solid bisphenol F type epoxy resin (softening point 108 ° C., manufactured by Mitsubishi Chemical Corporation, product name "jER4007P").
<Ingredient (B)>
jER807: Liquid bisphenol F type epoxy resin (epoxy equivalent 170 g / eq, manufactured by Mitsubishi Chemical Corporation, product name "jER807").
<Component (C)>
Triacrylate triacrylate tricyclodecanedimethanol diacrylate bisphenol A diglycidyl ether acrylic acid adduct pentaerythritol tetraacrylate dipentaerythritol hexaacrylate <component (d1)>
1400F: dicyandiamide (active hydrogen equivalent 21 g / eq, manufactured by Air Products & Chemicals, product name "DICYANEX 1400F").
DCMU-99: 3- (3,4-dichlorophenyl) -1,1-dimethylurea (manufactured by Hodogaya Chemical Co., Ltd., product name "DCMU-99").
<Component (d2)>
Dicumyl peroxide (10 hour half-life temperature 116.4 ° C).
<Ingredient (E)>
BYK-378: Polyether-modified polydimethylsiloxane (manufactured by Big Chemie Japan Co., Ltd., product name "BYK-378").
<Other surface conditioners>
BYK-DYNWET 800N: Alcohol alkoxylate (manufactured by Big Chemie Japan Co., Ltd., product name "BYK-DYNWET 800N").
<Ingredient (H)>
TSR-400: Oxazolidene type epoxy resin (epoxy equivalent 338 g / eq, manufactured by DIC Corporation, product name "TSR-400").
<Ingredient (I)>
Vinilec E: Polyvinyl formal resin (manufactured by JNC Corporation, product name "Vinirec E").
<Carbon fiber>
TR: Mitsubishi Chemical Corporation, product name "Pyrofil TR50S15L".
MR: Mitsubishi Chemical Corporation, product name "Pyrofil MR70 12P".

(Example 1)
Component (A) jER4007P, component (B) jER807, component (C1) ethoxylated isocyanuric acid triacrylate, component (C2) pentaerythritol tetraacrylate, component (d1) 1400F and DCMU-99, component (d2) A curable resin composition was prepared as follows, using dicumyl peroxide as the component (I), Vinilec E as the component (I), TSR-400 as the component (H), and BYK-378 as the component (E). First, according to the composition shown in Table 1, the component (B) (liquid) and the component (d1) (solid) are weighed and stirred in a container so that the mass ratio of the solid component and the liquid component is 1: 1. , Mixing to create a masterbatch containing component (D). This was further finely mixed with a three-roll mill to obtain a masterbatch containing a curing agent.
Subsequently, among the compositions shown in Table 1, the component (A) and the components (B), components (I), and components (H) other than those used in the masterbatch containing the curing agent were weighed in a flask, and an oil bath was placed. It was heated to 150 ° C. and dissolved and mixed. After that, when cooled to about 65 ° C., the component (C1) and the component (C2), the masterbatch containing the curing agent, the component (d2), and the component (E) are added and mixed by stirring to form an uncured curable resin composition. I got something. Various measurements and evaluations were carried out on the obtained uncured curable resin composition, the resin plate, the resin plate, and the prepreg prepared by using the curable resin composition. The results are shown in Table 1.

"Making a resin plate"
The uncured curable resin composition is injected between two glass plates, formed into a plate shape, heated at 2 ° C./min, held at an oven atmosphere temperature of 130 ° C. for 90 minutes, and cured by heating. , A resin plate having a thickness of 2 mm was produced.

"Making prepreg"
The uncured curable resin composition was made into a film with a comma coater (manufactured by HIRANO TECSEED Co., Ltd., "M-500"), and ^{a resin film having a resin texture of 16.7 g / m 2} was prepared on the release paper to prepare the release paper. A protective film made of polyethylene having a thickness of 17 μm was attached to the surface on which the surface was not placed. This resin film was laminated on both sides of a carbon fiber sheet having a fiber grain of 100 g / m ² obtained by arranging carbon fibers and impregnated with a heating roll to have a prepreg grain of 133.4 g / m ² and a resin content of 25. A mass% uncured unidirectional prepreg was obtained.

"Creation of fiber reinforced plastic plate"
The uncured prepreg having a resin content of 25% by mass obtained above was cut into a size of 300 mm × 300 mm, and 24 sheets were stacked with the fiber directions aligned to obtain a laminate. This laminate is heated in an autoclave at 2 ° C./min at a pressure of 0.04 MPa, held at 80 ° C. for 60 minutes, then heated at 2 ° C./min under a pressure of 0.6 MPa, and held at 130 ° C. for 90 minutes. Then, it was heat-cured to obtain a fiber-reinforced plastic plate having a thickness of 2.1 mm.

"Measurement of bending strength, flexural modulus, and breaking elongation (breaking strain) of resin plate"
The resin plate having a thickness of 2 mm obtained in the above "manufacturing of a resin plate" was processed into a test piece having a length of 60 mm and a width of 8 mm. The test piece is universally equipped with a three-point bending jig (indenter R = 3.2 mm, support R = 3.2 mm, distance between supports (L) = 32 mm) in an environment of a temperature of 23 ° C. and a humidity of 50% RH. Using a testing machine (“INSTRON 5565” manufactured by INSTRON), the bending strength, flexural modulus, and breaking elongation (breaking strain) of the resin plate were measured under the condition of a crosshead speed of 2 mm / min.

"Measurement of 90 ° bending strength, flexural modulus, and breaking elongation (breaking strain) of fiber reinforced plastic"
The fiber-reinforced plastic plate having a thickness of 2.1 mm obtained in the above-mentioned "Preparation of fiber-reinforced plastic plate" was processed into a test piece having a length of 60 mm and a width of 12.7 mm. The test piece was equipped with a three-point bending jig (indenter R = 3.2 mm, support R = 3.2 mm) in an environment of a temperature of 23 ° C. and a humidity of 50% RH (manufactured by INSTRON, "INSTRON". 5565 ”), the ratio of the distance between supports (L) to the thickness (d) of the test piece L / d = 16, cross head speed (minute speed) = (L ² × 0.01) / (6 × d) ), The 90 ° bending strength, flexural modulus, and breaking elongation (breaking strain) of the fiber reinforced plastic plate were measured.

"Resin viscosity at 60 ° C"
The viscosity of the thermosetting resin composition was measured under the following conditions.
Equipment: Rheometer (Thermo Fisher Scientific, "MARS 40"),
Plate used: 25φ parallel plate,
Plate gap: 0.5 mm,
Measurement frequency: 10 rad / sec,
Measurement temperature: 60 ° C,
Measurement time: 30 minutes,
Stress: 300 Pa
After heating to 60 ° C. under the above measurement conditions, the sample was placed on a plate and the isothermal viscosity was measured, and the minimum viscosity was defined as the resin viscosity at 60 ° C.

(Comparative Examples 1 to 5)
A curable resin composition was prepared in the same manner as in Example 1 except that the composition ratio was changed as in the compounding composition shown in Table 1, a resin plate, a resin film, and a prepreg were prepared, and various measurements and measurements were performed. Evaluation was performed. The evaluation results are shown in Table 1.

As shown in Table 1, each Example was superior in evaluation of bending strength or breaking strain as compared with Comparative Example containing no component (C1) or (C2). It is understood that the resin compositions and prepregs of the examples of the present application are highly compatible with strength and toughness.

By using the curable resin composition of the present invention, an excellent fiber reinforced plastic can be obtained. Therefore, according to the present invention, it is possible to provide a wide range of fiber-reinforced plastic molded articles having excellent mechanical properties, from molded articles for sports / leisure applications such as shafts for golf clubs to molded articles for industrial applications such as aircraft.

Claims (26)

A prepreg containing carbon fibers and a matrix resin, wherein the matrix resin contains the following components (A), (B), (C1), (C2), and (D).
Component (A): Bisphenol type epoxy resin with a softening point of 80 ° C or higher,
Ingredient (B): Bisphenol type epoxy resin liquid at 25 ° C,
Component (C1): (meth) acrylate having a cyclic structure,
Component (C2): (meth) acrylate having a chain structure,
Ingredient (D): Hardener. The prepreg according to claim 1, wherein the matrix resin contains a compound having a component (E): polysiloxane structure. The prepreg according to claim 1 or 2, wherein the matrix resin contains a component (H): an oxazolidone type epoxy resin. The component (C1) has at least one partial structure selected from the group consisting of a molecular structure including a benzene skeleton, an isocyanuric acid skeleton, a dicyclopentadiene skeleton, a biphenyl skeleton, a phenylbenzoate skeleton, an azobenzene skeleton, and a stilbene skeleton. The prepreg according to any one of claims 1 to 3. The prepreg according to any one of claims 1 to 4, wherein the component (C1) is an ethoxylated isocyanuric acid triacrylate, a tricyclodecanedimethanol diacrylate, or a bisphenol A diglycidyl ether acrylic adduct. The prepreg according to any one of claims 1 to 5, wherein the component (C2) is pentaerythritol tetraacrylate or dipentaerythritol hexaacrylate. The prepreg according to any one of claims 1 to 6, wherein the component (C1) and the content mass ratio (C1 / C2) of the component (C2) are 2.0 or more and 20 or less. A curable resin composition containing the following components (A1), (C1), (C2), and (D).
Ingredient (A1): Epoxy resin,
Component (C1): (meth) acrylate having a cyclic structure,
Component (C2): (Meta) acrylate component having a chain structure (D): Curing agent. At least one component (C1) of the curable resin composition is selected from the group consisting of a molecular structure including a benzene skeleton, an isocyanuric acid skeleton, a dicyclopentadiene skeleton, a biphenyl skeleton, a phenylbenzoate skeleton, an azobenzene skeleton, and a stilbene skeleton. The curable resin composition according to claim 8, which has one partial structure. The curable resin composition according to claim 8 or 9, wherein the component (A1) contains the following components (A) and (B).
Component (A): Bisphenol type epoxy resin with a softening point of 80 ° C or higher,
Ingredient (B): A bisphenol type epoxy resin that is liquid at 25 ° C. The curable resin composition according to any one of claims 8 to 10, wherein the curable resin composition contains a component (H): an oxazolidone type epoxy resin. Claimed that the component (D) contains at least one component (d1) selected from the group consisting of dicyandiamides, ureas, imidazoles, and aromatic amines, and a component (d2) which is a radical polymerization initiator. Item 8. The curable resin composition according to any one of Items 8 to 11. The curable resin composition according to claim 12, wherein the component (d1) is contained in an amount of 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the curable resin composition. The 12th or 13th claim, wherein the component (d2) is contained in an amount of 0.1 part by mass or more and 5 parts by mass or less with respect to a total of 100 parts by mass of all (meth) acrylate compounds contained in the curable resin composition. Curable resin composition. The curable resin composition according to claim 10, wherein the component (A) is contained in an amount of 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the curable resin composition. The curable resin composition according to claim 10, wherein the component (B) is contained in an amount of 20 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the curable resin composition. Any one of claims 8 to 16, wherein the components (C1) and (C2) are contained in a total of 5 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the curable resin composition. The curable resin composition according to. The curable resin composition according to any one of claims 8 to 17, wherein the content mass ratio (C1 / C2) of the component (C1) and the component (C2) is 2.0 or more and 20 or less. Component (I): The curable resin composition according to any one of claims 8 to 18, which comprises a thermoplastic resin. The curable resin composition according to claim 19, wherein the component (I) is contained in an amount of 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total epoxy resin contained in the curable resin composition. A film formed from the curable resin composition according to any one of claims 8 to 20. A molded product formed from a cured product of the curable resin composition according to any one of claims 8 to 20. A prepreg in which an aggregate of reinforcing fibers is impregnated with the curable resin composition according to any one of claims 8 to 20. A fiber-reinforced plastic comprising a cured product of the curable resin composition according to any one of claims 8 to 20 and reinforcing fibers. The fiber-reinforced plastic according to claim 24, wherein the reinforcing fiber is carbon fiber. The fiber reinforced plastic according to claim 24 or 25, which is tubular.