Epoxy resin composition and prepreg

Abstract

The present invention addresses the problem of providing a resin composition having exceptional light resistance, and a prepreg that has exceptional light resistance and handleability at room temperature and that has less resin flow during curing. In order to overcome the above problem, the present invention provides a resin composition having the constitution disclosed below. 　An epoxy resin composition containing constituent elements [A], [B], [C], and [D], a non-aromatic epoxy resin represented by formula (I) in which n is 1 representing at least 95 mass% of the total mass of constituent element [B]. [A] A non-aromatic epoxy resin other than constituent element [B]. [B] A non-aromatic epoxy resin represented by formula (I). R1 is any group ("non-aromatic organic group") from among divalent groups in which a non-aromatic hydrocarbon and a non-aromatic hydrocarbon group are linked via an ether group or an amino group (–NR–; where R is a non-aromatic hydrocarbon group). R2 and R3 are non-aromatic organic groups in which the hydrogen atom of the non-aromatic hydrocarbon group thereof is substituted by at least one epoxy group and at least one hydroxyl group. Each of R4 and R5 is a non-aromatic organic group in which the hydrogen atom of the non-aromatic hydrocarbon group is substituted by at least one epoxy group and at least one hydroxyl group, a non-aromatic hydrocarbon group forming part of a nitrogen-containing heterocycle, or a hydrogen atom. In formula (I), n is an integer from 1 to 5, and each of R1, R2, R3, R4, and R5 is a hydrogen atom, or a linear, a branched, or a cyclic structure. [C] A curing agent. [D] A non-aromatic thermoplastic resin.

Description

[Technical Field]

[0001] The present invention relates to an epoxy resin composition having excellent light resistance, and a prepreg using the epoxy resin composition having excellent light resistance and having good handleability. [Background technology]

[0002] Prepregs, which are made by impregnating a fiber substrate with a thermosetting resin such as epoxy resin, are often used in products requiring high structural performance, such as aircraft structural components, wind turbine blades, automobile exterior panels, and computer applications such as IC trays and laptop computer housings. However, fiber composite materials obtained by curing typical prepregs have poor light resistance and deteriorate or degrade when exposed to light. For this reason, there has been an increasing demand in recent years for fiber composite material surfaces that can be made light resistant. Patent Document 1 proposes an epoxy resin that does not contain an aromatic ring as a resin composition with light resistance. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-26763 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the non-aromatic epoxy resins described in Patent Document 1 generally have weak intermolecular interactions and therefore low viscosity. Therefore, resin films made from non-aromatic epoxy resins and prepregs made by impregnating a fiber substrate with such resin films have problems in that they are difficult to handle at room temperature and are prone to resin flow during curing and molding.

[0005] Therefore, an object of the present invention is to provide a resin composition that has excellent light resistance and that, when used as a prepreg, has excellent handleability at room temperature. Another object of the present invention is to provide a prepreg that has excellent light resistance and, in a preferred embodiment, has even better handleability at room temperature and exhibits little resin flow during curing and molding. [Means for solving the problem]

[0006] In order to solve the above problems, the present invention provides a resin composition having the following configuration.

[0007] The composition contains components [A], [B], [C], and [D], and the non-aromatic epoxy resin of formula (I) in which n is 1 accounts for 95 mass% or more of the total mass of component [B]. and the number average molecular weight of the epoxy resin mixture of component [A] and component [B] is 450 to 800 g / mol. , epoxy resin composition. [A] Non-aromatic epoxy resin other than component [B] [B] Non-aromatic epoxy resin represented by formula (I)

[0008] [ka]

[0009] where R 1 is a divalent non-aromatic hydrocarbon group or a group formed by linking non-aromatic hydrocarbon groups via an ether group or an amino group (-NR-, where R is a non-aromatic hydrocarbon group) (hereinafter, "non-aromatic hydrocarbon groups and groups formed by linking non-aromatic hydrocarbon groups via an ether group or an amino group (-NR-, where R is a non-aromatic hydrocarbon group)" are collectively referred to as "non-aromatic organic groups"), and R 2 and R 3 is a non-aromatic organic group in which at least one epoxy group and at least one hydroxyl group have substituted hydrogen atoms of the non-aromatic hydrocarbon group, and R 4 and R 5is a non-aromatic organic group in which the hydrogen atoms of the non-aromatic hydrocarbon group are substituted with at least one epoxy group and at least one hydroxyl group, a non-aromatic hydrocarbon group that forms part of a nitrogen-containing heterocycle, or a hydrogen atom. In formula (I), n is an integer of 1 to 5, and R 1 , R 2 and R 3 is a linear, branched or cyclic structure; R 4 and R 5 is a hydrogen atom, a straight chain, branched or cyclic structure. [C] Hardener [D] Non-aromatic thermoplastic resin Another aspect of the present invention for solving the above problems is a resin composition having the following constitution.

[0010] An epoxy resin composition comprising components [G], [C], and [D'] and having the following properties 1 and 2: [G] A mixture of epoxy resins containing at least one non-aromatic epoxy resin and having a number average molecular weight of 550 to 800 g / mol. [C] Hardener [D'] Non-aromatic thermoplastic resin with a number average molecular weight of 16,000 to 28,000 g / mol Property 1: After degassing in a vacuum, the resin is heated at a rate of 2°C / min and held at 180°C for 120 minutes to harden, resulting in a 2mm thick cured resin plate with a bending fracture strain of 4.5% or more. Property 2: The epoxy resin composition does not contain a non-aromatic epoxy resin represented by formula (I).

[0011] [ka]

[0012] where R 1 is a divalent non-aromatic organic group, and R 2 and R 3 is a non-aromatic organic group in which at least one epoxy group and at least one hydroxyl group have substituted hydrogen atoms of the non-aromatic hydrocarbon group, and R 4 and R5 is a non-aromatic organic group in which the hydrogen atoms of the non-aromatic hydrocarbon group are substituted with at least one epoxy group and one hydroxyl group, a non-aromatic hydrocarbon group that forms part of a nitrogen-containing heterocycle, or a hydrogen atom. In formula (I), n is an integer of 1 to 5, and R 1 , R 2 and R 3 is a linear, branched or cyclic structure; R 4 and R 5 is a hydrogen atom, a straight chain, branched or cyclic structure. [Effects of the Invention]

[0013] The present invention provides an epoxy resin composition that has excellent light resistance and excellent handleability at room temperature when used as a prepreg. A resin film formed from the epoxy resin composition of the present invention and a prepreg obtained by impregnating a fiber substrate with the resin film have excellent light resistance, and in a preferred embodiment, exhibit excellent handleability at room temperature and the effect of reducing resin flow during curing and molding. DETAILED DESCRIPTION OF THE INVENTION

[0014] Each component of the resin composition of the present invention will be described in detail below. In the present invention, "aromatic" refers to a compound containing an aromatic hydrocarbon group or a conjugated unsaturated heterocycle in its chemical structure, i.e., a compound having a conjugated unsaturated ring structure that satisfies Hückel's rule; anything other than this is "non-aromatic." Furthermore, when essential or preferred ranges for a certain physical property or characteristic are expressed as multiple numerical ranges, a preferred range can also be defined as a combination of any upper limit and any lower limit in those ranges (for example, a preferred range for the number-average molecular weight of the non-aromatic epoxy resin or its mixture described below could be 600 to 800 g / mol).

[0015] The epoxy resin composition of the present invention is an epoxy resin composition using a non-aromatic epoxy resin as the epoxy resin, and when the total amount of epoxy resins is taken as 100 mass %, the non-aromatic epoxy resin preferably accounts for 90% or more, more preferably 95% or more, and may even account for 100%.

[0016] "Component [A]" Component [A] is a non-aromatic epoxy resin that does not fall under the category of component [B] described below, and can also be a mixture of multiple such epoxy resins. Examples of epoxy resins that fall under component [A] include alicyclic epoxy resins (epoxy resins containing a cycloalkane ring) such as tetrahydroindene diepoxide, vinylcyclohexene oxide, dipentene dioxide, dicyclopentadiene dioxide, bis(2,3-epoxycyclopentyl)ether, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, bi-7-oxabicyclo[4.1.0]heptane, dodecahydrobisphenol A diglycidyl ether, dodecahydrobisphenol F diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, and 2,2-bis(4-hydroxycyclohexyl)propanodiglycidyl ether. Specific examples of epoxy resins that do not contain aromatic rings, aminic nitrogen atoms, cycloalkane rings, or cycloalkene rings include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol glycidyl ether, 1,6-hexanediol diglycidyl ether, neopentylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, 1,4-bis(2-oxiranyl)butane, and pentaerythritol polyglycidyl ether. Specific examples of monofunctional epoxy compounds (epoxy compounds containing only one oxirane ring) that do not contain aromatic rings or aminic nitrogen atoms include 4-tert-butyl glycidyl ether, butyl glycidyl ether, 1-butene oxide, 1,2-epoxy-4-vinylcyclohexane, and 2-ethylhexyl glycidyl ether.

[0017] The combination of the above non-aromatic epoxy resins or mixtures thereof is not particularly limited in the present invention. From the viewpoint of heat resistance, the non-aromatic epoxy resin of component [A] is preferably an alicyclic epoxy resin or an epoxy resin having a cycloalkane structure such as a cyclohexane ring in the molecule.

[0018] The non-aromatic epoxy resin may be commercially available, such as EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.), THI-DE (manufactured by JXTG Nippon Oil & Energy Corporation), TTA22 (manufactured by Sun Chemical Co., Ltd.), Ex-121, Ex-211, Ex-212, Ex-313, Ex-321, and Ex-411 (manufactured by Nagase Chemtec Corporation), Epolite (registered trademark) 4000 (manufactured by Kyoeisha Chemical Co., Ltd.), ST-3000 and ST-4000 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), YX8000 (manufactured by Mitsubishi Chemical Corporation), and EPALOY5000 (manufactured by Huntsman).

[0019] "Component [B]"

[0020] [ka]

[0021] The component [B] is a non-aromatic epoxy resin having a structure represented by formula (I), which contains at least two hydroxyl groups and at least two epoxy groups in its molecular structure, and also has a secondary amino group or a tertiary amino group in its molecular structure. 1 is a divalent non-aromatic organic group, and R 2 and R 3 is a monovalent non-aromatic organic group in which at least one epoxy group and at least one hydroxyl group have substituted hydrogen atoms of the non-aromatic hydrocarbon group, and R 4 and R 5is a monovalent non-aromatic organic group in which the hydrogen atoms of the non-aromatic hydrocarbon group are substituted with at least one epoxy group and at least one hydroxyl group, a non-aromatic hydrocarbon group that forms part of a nitrogen-containing heterocycle, or a hydrogen atom. In formula (I), n is an integer of 1 to 5, preferably an integer of 1 or 2, and the non-aromatic epoxy resin of formula (I) in which n is 1 accounts for 95 mass % or more of the total mass of component [B]. 1 , R 2 and R 3 is a linear, branched or cyclic structure; R 4 and R 5 R may be a hydrogen atom, a straight chain, branched or cyclic structure. 2 , R 3 , R 4 and R 5 The epoxy group is preferably a glycidyl group or an alicyclic epoxy group. The "non-aromatic organic group" is preferably a non-aromatic hydrocarbon group. When non-aromatic hydrocarbon groups are linked via an ether group or an amino group (-NR-, where R is a non-aromatic hydrocarbon group), the number of linked non-aromatic hydrocarbon groups may be three or more. Furthermore, the R substituted on the amino group may form part of a cyclic structure.

[0022] Component [B] can be obtained, for example, by reacting a non-aromatic epoxy compound (including resins; the same applies below) with a non-aromatic amine. Such non-aromatic epoxy compounds have multiple epoxy groups, and examples of the resins exemplified for component [A] described above can be used. Specific examples of non-aromatic amines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, 4,4'-methylenebis(2-methylcyclohexylamine), isopropyldiamine, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, methoxypoly(oxyethylene / oxypropylene)-2-propylamine, polyoxypropylenediamine, polyetheramine, triethyleneglycoldiamine, trimethylolpropanepoly(oxypropylene)triamine, and glycerylpoly(oxypropylene)triamine. Those that react with the non-aromatic epoxy compound to form the above structure are selected.

[0023] The combination of non-aromatic epoxy compound and non-aromatic amine used in the reaction to obtain component [B] is not particularly limited in the present invention, as long as it is a combination that gives an epoxy resin having the structure represented by formula (I). To produce the structure of formula (I), the molar ratio of the reaction of non-aromatic epoxy compound and non-aromatic amine is preferably 1.0 parts non-aromatic epoxy compound to 0.1 to 0.5 parts non-aromatic amine. Within this range, component [B] contains at least two epoxy groups in its structure, and therefore can function as a thermosetting resin.

[0024] Furthermore, the curing reaction can be completed without gelation. The reaction is preferably carried out by heating, and a catalyst may be used in the reaction. The reaction is preferably carried out by stirring the non-aromatic epoxy compound and the non-aromatic amine at 80 to 180°C for 1 to 12 hours, more preferably at 80 to 150°C for 1 to 5 hours. The reaction is preferably carried out as a preliminary reaction in a system that does not contain a curing agent, and an epoxy resin composition can be obtained by adding a curing agent or the like to the reaction product containing the component [A] and the component [B]. From the viewpoint of heat resistance, the non-aromatic epoxy compound and the non-aromatic amine preferably have an alicyclic or cycloalkane structure such as a cyclohexane ring in the molecule.

[0025] The non-aromatic epoxy compound and non-aromatic amine may be commercially available. In one preferred embodiment, the non-aromatic epoxy compound is the same resin as the non-aromatic epoxy resin used in component [A]. Examples of non-aromatic amines include EDA (ethylenediamine), DETA (diethylenetriamine), TETA (triethylenetetramine), TEPA (tetraethylenepentamine), PEHA (pentaethylenehexamine), AEP (aminoethylpiperazine) (Tosoh Corporation), Ramiron C-260, IPDA (isophoronediamine) (BASF), Wondamin HM (New Japan Chemical Co., Ltd.), VESTAMIN® PACM (Evonik Japan Co., Ltd.), 1,3-BAC (Mitsubishi Gas Chemical Company, Inc.), and JEFFAMINE® (HUNTSMAN).

[0026] The number-average molecular weight of the component [A] and the component [B] in a mixture of the component [A] and the component [B] is preferably in the range of 450 to 800 g / mol. The combination and composition ratio of these components are not particularly limited in the present invention. From the viewpoints of ease of forming a resin film and the tackiness of the prepreg produced by impregnating a fiber substrate with the resin film, the number-average molecular weight of the mixture of the component [A] and the component [B] is preferably 550 to 700 g / mol. It is even more preferably 600 to 700 g / mol. A number-average molecular weight of 800 g / mol or less is preferred because the viscosity of the epoxy resin composition does not become too high, facilitating the formation of a resin film by the hot melt method. On the other hand, a number-average molecular weight of 450 g / mol or more is preferred because the viscosity of the epoxy resin composition does not become too low, and the prepreg produced by impregnating a fiber substrate with a resin film made from the resin composition does not become excessively tacky. Here, the number-average molecular weight refers to the number-average molecular weight in terms of polystyrene as determined by gel permeation chromatography.

[0027] "Component [C]" The epoxy resin composition of the present invention contains a curing agent (component [C]). The type of curing agent is not particularly limited, and examples include amine-based curing agents, imidazoles, cationic curing agents, acid anhydrides, and boron chloride amine complexes. From the viewpoint of light resistance, it is preferable to use a non-aromatic curing agent. A non-aromatic curing agent refers to a curing agent that does not contain an aromatic hydrocarbon group or an unsaturated heterocycle in its chemical structure. Among these, dicyandiamide is preferred because it prevents performance changes due to moisture in the epoxy resin composition before curing and allows curing to be completed at a relatively low temperature while maintaining long-term stability.

[0028] The curing agent may be a commercially available product. For example, dicyandiamide may be "jER Cure (registered trademark)" DICY7 or DICY15 (manufactured by Mitsubishi Chemical Corporation), imidazoles may be "Curezol 1.2DMZ", "C11Z" or "C17Z" (manufactured by Shikoku Kasei Co., Ltd.), and cationic curing initiators may be "Adeka Opton (registered trademark)" CP-77, "Adeka Opton (registered trademark)" CP-66 (manufactured by ADEKA Corporation), CI-2639, CI-2624 (Nippon Soda), "Sanaide (registered trademark)" SI-60, ... Examples of suitable fluoride compounds include SAN-AID (registered trademark) SI-80, SAN-AID (registered trademark) SI-100, SAN-AID (registered trademark) SI-150, SAN-AID (registered trademark) SI-B4, and SAN-AID (registered trademark) SI-B5 (manufactured by Sanshin Chemical Industry Co., Ltd.), TA-100, and IK-1PC(80) (manufactured by San-Apro Co., Ltd.), and examples of suitable acid anhydrides include RIKACID (manufactured by New Japan Chemical Co., Ltd.), and examples of suitable boron trifluoride piperidine and boron chloride amine complexes include boron trifluoride monoethylamine (manufactured by Stella Chemifa Corporation).

[0029] The preferred amount of dicyandiamide to be blended is such that the number of moles of active hydrogen in dicyandiamide is 0.6 to 1.2 times the number of moles of epoxy groups derived from all epoxy resins blended into the epoxy resin composition, from the viewpoint of obtaining a cured product that exhibits good mechanical properties. A blending amount of 0.7 to 1.0 times is even more preferred, as it provides excellent heat resistance.

[0030] "Component [D]" The epoxy resin composition of the present invention contains a non-aromatic thermoplastic resin (component [D]). A non-aromatic thermoplastic resin refers to a non-aromatic thermoplastic resin. The term "non-aromatic" is as described above. Examples of non-aromatic thermoplastic resins include polyvinyl alcohol and its acetal compounds. Examples of non-aromatic thermoplastic resins include polyvinyl alcohol, acetal compounds of polyvinyl alcohol such as polyvinyl acetal, polyvinyl formal, polyvinyl acetoacetal, and polyvinyl butyral, as well as polyvinyl acetate, hydrogenated bisphenol A-pentaerythritol phosphite polymer, hydrogenated terpene, and hydrogenated terpene phenol.

[0031] Among the above, polyvinyl alcohol and its acetal compounds, polyvinyl acetals (polyvinyl acetoacetal, polyvinyl butyral, polyvinyl formal) or polyvinyl vinyl acetate, which have high solubility in non-aromatic epoxy resins, are particularly preferred in that they allow easy adjustment of the viscosity of the epoxy resin composition.

[0032] Furthermore, from the viewpoints of ease of film formation and tackiness of prepregs produced by impregnating a fiber substrate with the resin film, the number-average molecular weight of these non-aromatic thermoplastic resins is preferably 16,000 to 28,000 g / mol. It is more preferably 17,000 to 27,000 g / mol, and even more preferably 18,000 to 27,000 g / mol. If the number-average molecular weight of the non-aromatic thermoplastic resin exceeds 28,000 g / mol, the viscosity increase of the epoxy resin composition per added amount of non-aromatic thermoplastic resin may be significant. Therefore, from the viewpoints of ease of film formation and tackiness control, it is necessary to reduce the amount of added non-aromatic thermoplastic resin. However, the lower the amount of added thermoplastic resin, the lower the bending break strain of the cured resin. On the other hand, if the number-average molecular weight of the non-aromatic thermoplastic resin is less than 16,000 g / mol, the viscosity increase of the epoxy resin composition per added amount of non-aromatic thermoplastic resin may be small, resulting in excessive film tackiness and a decrease in the elastic modulus of the cured resin. When the number average molecular weight of the non-aromatic thermoplastic resin is 16,000 to 28,000 g / mol, the resin composition can be easily formed into a film, and the cured resin can have a good balance of tackiness, breaking strain, and elastic modulus. The number average molecular weight here means the number average molecular weight in terms of polystyrene measured by gel permeation chromatography.

[0033] The non-aromatic thermoplastic resin may be a commercially available product, such as "J-POVAL (registered trademark)" (manufactured by Nippon Vinyl Acetate Poval Co., Ltd.), "S-LEC (registered trademark)" (manufactured by Sekisui Chemical Co., Ltd.), "Ultrasene (registered trademark)" (manufactured by Tosoh Corporation), "JPH-3800" (manufactured by Johoku Chemical Industry Co., Ltd.), or "YS Polystar UH130" (manufactured by Yasuhara Chemical Co., Ltd.).

[0034] The content of the non-aromatic thermoplastic resin is preferably 1 to 20 parts by mass, based on 100 parts by mass of the total of components [A] and [B], from the viewpoints of ease of film formation and tackiness of the prepreg produced by impregnating the resin film into a fiber substrate, and more preferably 5 to 15 parts by mass.

[0035] "Component [E]" The epoxy resin composition of the present invention may contain a curing accelerator (component [E]). Examples of the curing accelerator include urea-based curing accelerators, hydrazide-based curing accelerators, tertiary amines, imidazoles, and phenols. In particular, when component [C] is dicyandiamide, a urea-based curing accelerator is preferred from the viewpoints of curing acceleration and storage stability at room temperature.

[0036] The curing accelerator may be a commercially available product, such as DCMU99 (manufactured by Hodogaya Chemical Co., Ltd.), "Omicure (registered trademark)" U-24M, U-52M (manufactured by CVC Thermoset Specialties), UDH-J (manufactured by Ajinomoto Fine-Techno Co., Ltd.), CDH, MDH, SUDH, ADH, SDH (manufactured by Nippon Finechem Co., Ltd.), "DDH-S, IDH-S" (manufactured by Otsuka Chemical Co., Ltd.), or "Kao Raiser (registered trademark)" No. 20 (manufactured by Kao Corporation).

[0037] The amount of the curing accelerator is preferably 0.1 to 5 parts by mass, more preferably 1 to 3 parts by mass, based on 100 parts by mass of the total of the components [A] and [B], from the viewpoints of curing acceleration and storage stability at room temperature.

[0038] "Component [F]" The epoxy resin composition of the present invention may contain inorganic particles (component [F]). Examples of inorganic particles include inorganic particles that exhibit thixotropic properties when incorporated (sometimes referred to as "thixotropic agents" in this specification), pigments, etc.

[0039] Examples of thixotropic agents include silicon dioxide, synthetic hectorite, clay minerals, modified bentonite, and mixed systems of mineral and organically modified bentonite.

[0040] The thixotropic agent may be a commercially available product, and examples thereof include fumed silica (Aerosil (registered trademark) 50, 90G, 130, 150, 200, 300, 380, RY200S, Aeroxide (registered trademark) AluC, Alu65, Alu130, TiO2T805 (manufactured by Nippon Aerosil Co., Ltd.)), OPTIGEL (registered trademark) WX, OPTIBENT (registered trademark) 616, GARAMITE (registered trademark) 1958, 7305, LAPONITE (registered trademark) S-482, TIXOGEL (registered trademark) MP, VP, CRAYTONE (registered trademark) 40, CLOISITE (registered trademark) 20A (manufactured by BYK Corporation), Somasif (registered trademark) ME-100, Micromica MK (manufactured by Katakura Co-op Agri Co., Ltd.).

[0041] The amount of the thixotropic agent is preferably 1 to 10 parts by mass, more preferably 3 to 8 parts by mass, based on 100 parts by mass of the total of the components [A] and [B], from the viewpoints of ease of film formation and suppression of resin flow during curing and molding.

[0042] Examples of pigments include barium sulfate, zinc sulfide, titanium oxide, aluminum oxide, molybdenum red, cadmium red, chromium oxide, titanium yellow, cobalt green, cobalt blue, ultramarine, barium titanate, carbon black, iron oxide, red phosphorus, and copper chromate.

[0043] The pigments may be commercially available products, and examples thereof include B-30, BARIFINE BF (manufactured by Sakai Chemical Industry Co., Ltd.), "Ti-Pure (registered trademark)" TS-6200, R-902+, R-960, R-706 (manufactured by Chemours Corporation), and "Aeroxide (registered trademark)" (manufactured by Nippon Aerosil Co., Ltd.).

[0044] The blending amount of the pigment is preferably 15 to 50 parts by mass, more preferably 20 to 40 parts by mass, based on 100 parts by mass of the total of the components [A] and [B], from the viewpoints of ease of film formation and light resistance.

[0045] "Component [G]" The component [G] is a mixture of epoxy resins containing at least one non-aromatic epoxy resin, and the mixture has a number average molecular weight of 550 to 800 g / mol.

[0046] The combination of epoxy resins in the component [G] is not particularly limited as long as it has a number average molecular weight in the range of 550 to 800 g / mol and contains at least one non-aromatic epoxy resin.

[0047] Specifically, by using a non-aromatic thermoplastic resin (component [D']) having a number-average molecular weight of 16,000 to 28,000 g / mol in combination with the composition and further providing the following properties 1 and 2, it is possible to achieve excellent handleability at room temperature and suppression of resin flow during curing and molding. Furthermore, from the viewpoints of ease of film formation and the tackiness of the prepreg produced by impregnating a fiber substrate with the resin film, the number-average molecular weight of component [G] is preferably 550 to 700 g / mol. It is more preferably 600 to 700 g / mol. If the number-average molecular weight exceeds 800 g / mol, the viscosity of the epoxy resin composition becomes high, making it difficult to form a resin film by the hot melt method. Furthermore, the tackiness of the prepreg produced by impregnating a fiber substrate with a resin film made from the resin composition decreases. On the other hand, if the number-average molecular weight of the component [G] is less than 550 g / mol, the viscosity of the epoxy resin composition will be low, resulting in excessive tackiness of the prepreg obtained by impregnating a fiber substrate with a resin film made from the resin composition. If the number-average molecular weight of the component [G] is 550 to 800 g / mol, a good balance between ease of resin film formation and tackiness will be achieved. Here, the number-average molecular weight refers to the number-average molecular weight calculated as polystyrene by gel permeation chromatography. From the viewpoint of heat resistance, it is preferable to use a non-aromatic epoxy resin that is an alicyclic epoxy or one having a cycloalkane structure such as a cyclohexane ring in the molecule.

[0048] In the component [G], commercially available non-aromatic epoxy resins can be used. For example, "Celloxide (registered trademark)" 2021P, "Celloxide (registered trademark)" 8010, "Celloxide (registered trademark)" 2000, "Epolead (registered trademark)" GT401, "Celloxide (registered trademark)" 2081, EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.), THI-DE (manufactured by JXTG Nippon Oil & Energy Corporation), TTA21, AAT15, and TTA22 (manufactured by Sun Chemical Co., Ltd.). ), Ex-121, Ex-211, Ex-212, Ex-313, Ex-321, Ex-411 (manufactured by Nagase Chemtec Corporation), Epolite (registered trademark) 4000 (manufactured by Kyoeisha Chemical Co., Ltd.), ST-3000, ST-4000 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), YX8000 (manufactured by Mitsubishi Chemical Corporation), and EPALOY5000 (manufactured by HUNTSMAN).

[0049] In component [G], the non-aromatic epoxy resin is preferably contained in an amount of 90 to 100 parts by mass, assuming that the mass of the total epoxy resin is 100 parts by mass, thereby achieving high light resistance. Furthermore, when only epoxy resins having an alicyclic epoxy structure or a cycloalkane structure such as a cyclohexane ring in the molecule are used as the epoxy resin, an epoxy resin cured product having both light resistance and a high glass transition temperature can be obtained.

[0050] Furthermore, when component [G] is used, the epoxy resin composition of the present invention contains the above-mentioned components [C] and [D'], and also has the following properties 1 and 2. By making the epoxy resin satisfy the following properties, it is possible to achieve excellent handleability at room temperature and suppression of resin flow during curing and molding.

[0051] Property 1: After degassing in a vacuum, the resin is heated at a rate of 2°C / min and held at 180°C for 120 minutes to harden, resulting in a 2mm thick cured resin plate with a bending fracture strain of 4.5% or more.

[0052] Property 2: The epoxy resin composition does not contain a non-aromatic epoxy resin represented by formula (I).

[0053] [ka]

[0054] where R 1 is a divalent non-aromatic organic group, and R 2 and R 3 is a non-aromatic organic group in which at least one epoxy group and at least one hydroxyl group have substituted hydrogen atoms of the non-aromatic hydrocarbon group, and R 4 and R 5 is a non-aromatic organic group in which the hydrogen atoms of the non-aromatic hydrocarbon group are substituted with at least one epoxy group and at least one hydroxyl group, a non-aromatic hydrocarbon group that forms part of a nitrogen-containing heterocycle, or a hydrogen atom. In formula (I), n is an integer of 1 to 5, preferably an integer of 1 or 2, and R 1 , R 2 and R 3 is a linear, branched or cyclic structure; R 4 and R 5 is a hydrogen atom, a straight chain, branched or cyclic structure.

[0055] "Other additives" The epoxy resin composition of the present invention may contain additives such as rubber, a flame retardant, a light stabilizer, an antioxidant, and a defoaming agent, if necessary.

[0056] Examples of rubber include natural rubber, diene rubber, and non-diene rubber. Examples of diene rubber include styrene-butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, and acrylonitrile-butadiene rubber. Examples of non-diene rubber include butyl rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, urethane rubber, silicone rubber, and fluororubber. Non-diene rubbers are preferred for inclusion in the epoxy resin composition of the present invention. Among these, ethylene-propylene rubber, ethylene-propylene-diene rubber, silicone rubber, and fluororubber, which do not have double bonds in the polymer backbone, are particularly preferred because they have high light resistance and little effect on the light resistance of the epoxy resin composition of the present invention. Furthermore, powder-like rubber is particularly preferred because it disperses well in the epoxy resin composition.

[0057] The amount of these additives to be added is preferably within a range that does not impair the inherent properties of the epoxy resin composition of the present invention, i.e., 50 parts by mass or less per 100 parts by mass of the total of constituent element [A] and constituent element [B], or 50 parts by mass or less per 100 parts by mass of constituent element [G].

[0058] "Prepreg" The epoxy resin composition of the present invention can be impregnated into a fiber substrate and used as a prepreg.

[0059] Examples of fiber substrates include carbon fiber, graphite fiber, aramid fiber, silicon carbide fiber, alumina fiber, boron fiber, high-strength polyethylene fiber, tungsten carbide fiber, PBO fiber, and glass fiber, which may be used alone or in combination of two or more. The fibers may be continuous fibers aligned in one direction, or may be a fabric substrate such as a woven or knitted fabric. A mat or nonwoven fabric in which discontinuous fibers are accumulated may also be used. There are no particular restrictions on the fiber basis weight of the prepreg of the present invention.

[0060] "Curing properties" From the viewpoint of storage stability, the epoxy resin composition of the present invention and the prepreg made from the resin composition preferably have a curing exothermic peak temperature measured by differential scanning calorimetry (DSC) of 100 to 250°C. From the viewpoint of surface smoothness obtained by low-temperature curing of the prepreg, a temperature of 100 to 150°C is more preferable.

[0061] "viscosity" From the viewpoints of ease of film formation, tackiness of the prepreg produced by impregnating a fiber substrate with the resin film, and resin flow during curing and molding, the viscosity of the epoxy resin composition of the present invention is preferably 40,000 Pa·s or more and 200,000 Pa·s or less at 30°C, 300 Pa·s or less at 80°C, and 100 Pa·s or more and 300 Pa·s or less at 100°C. When the viscosity of the epoxy resin composition is 40,000 Pa·s or more at 30°C, the tackiness of the prepreg produced by impregnating a fiber substrate with a resin film formed from the resin composition is preferably not excessive. When the viscosity is 200,000 Pa·s or less, the adhesion of the prepreg produced by impregnating a fiber substrate with a resin film formed from the resin composition is preferably good. Furthermore, an epoxy resin composition having a viscosity of 300 Pa·s or less at 80°C facilitates the formation of resin films by the hot-melt method, and a viscosity of 100 Pa·s or more at 100°C is preferred because it can adequately suppress resin flow in resin films formed from the resin composition and in prepregs formed by impregnating a fiber substrate with the resin film. An epoxy resin composition having a viscosity of 40,000 Pa·s or more to 200,000 Pa·s at 30°C, 300 Pa·s or less at 80°C, and 100 Pa·s or more to 300 Pa·s at 100°C provides a good balance of ease of forming resin films, tack, and resin flow. Viscosity here refers to the viscosity measured at a frequency of 0.5 Hz while increasing the temperature from 20°C to 150°C at a rate of 2°C / min.

[0062] "Lightfastness" The epoxy resin composition of the present invention is irradiated with ultraviolet light having a wavelength of 300 to 400 nm on a cured product thereof at a dose of 1000 kJ / m, which is known to be the approximate amount of UV light received in one month in Japan (summer). 2 From the viewpoint of light resistance, it is preferable that no discoloration is observed after irradiation. In the present invention, "no discoloration is observed" means that the difference in color ΔE * ab is 4 or less, and the formula difference ΔE * ab UV rays with wavelengths of 300-400 nm are emitted at 1000 kJ / m 2 The color values ​​of the cured product of the epoxy resin composition before and after irradiation can be determined by measuring them using a multi-light source spectrocolorimeter.

[0063] "Bending fracture strain" The epoxy resin composition of the present invention preferably has a bending strain at break of 4.5% or more as measured by the measurement test described below. There is no particular upper limit to the bending strain at break, but 7% is sufficient.

[0064] The bending strain at break is a value measured on a 2 mm thick cured resin plate obtained by degassing an epoxy resin composition in a vacuum, raising the temperature at a rate of 2°C / min, and holding it at 180°C for 120 minutes to cure it, and then performing three-point bending with a span of 32 mm according to JIS-K7171 (1994). The average value of six measurements is calculated. If the resin plate does not break in the resin bending test, the device is stopped when the bending deflection exceeds 12 mm, and this value is taken as the breaking strain. Detailed measurement procedures are described in the Examples section. [Example]

[0065] The present invention will be described in more detail below with reference to examples. However, the scope of the present invention is not limited to these examples. Furthermore, measurements of various properties were carried out in an environment of a temperature of 23°C and a relative humidity of 50%, unless otherwise noted.

[0066] <Materials used in Examples and Comparative Examples> (1) Aromatic epoxy resin Bisphenol A epoxy resin ("jER (registered trademark)" 828 (hereinafter "jER828"), manufactured by Mitsubishi Chemical Corporation) epoxy equivalent: 175 (g / eq.) (liquid) (2) Non-aromatic epoxy resin Hydrogenated bisphenol epoxy resin (EPALLOY 5000, manufactured by HUNTSMAN) Epoxy equivalent: 220 (g / eq.) (liquid) 2,2-bis(hydroxymethyl)-1-butanol to 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct (EHPE3150, Daicel Chemical Industries, Ltd.) Epoxy equivalent: 170-190 (g / eq.) (solid) (3) Non-aromatic amines 4,4'-methylenebis(cyclohexylamine) (mixture of isomers) (VESTAMIN® PACM (hereinafter referred to as PACM), manufactured by Evonik Japan Co., Ltd.) (4) Hardener Dicyandiamide ("jER Cure (registered trademark)" DICY7T (hereinafter "DICY7T"), manufactured by Mitsubishi Chemical Corporation) (5) Non-aromatic thermoplastic resin Polyvinyl acetoacetal ("S-LEC (registered trademark)" KS-10 (hereinafter referred to as "KS-10"), KS-1 (hereinafter referred to as "KS-1"), manufactured by Sekisui Chemical Co., Ltd., number average molecular weights of 17,000 g / mol and 27,000 g / mol) Polyvinyl butyral ("S-LEC (registered trademark)" BX-L (hereinafter referred to as "BX-L"), manufactured by Sekisui Chemical Co., Ltd., number average molecular weight 18,000 g / mol) Polyvinyl butyral ("S-LEC (registered trademark)" BL-10 (hereinafter "BL-10"), BL-5Z (hereinafter "BL-5Z"), BM-5 (hereinafter "BM-5"), manufactured by Sekisui Chemical Co., Ltd., number average molecular weights of 15,000 g / mol, 32,000 g / mol, and 56,000 g / mol) (6) Curing accelerator Toluene bis(dimethylurea) ("Omicure®" 24 (hereinafter "Omicure 24"), manufactured by CVC Thermoset Specialties) (7) Inorganic particles Fumed silica (Aerosil (registered trademark) RY200S (hereinafter referred to as "RY200S"), manufactured by Nippon Aerosil Co., Ltd.) Titanium oxide ("Ti-Pure (registered trademark)" R-960 (hereinafter referred to as "R-960"), manufactured by Chemours, Inc., average particle size 0.5 μm) (8) Fiber base material Polyester fiber nonwoven fabric (JH-30015, manufactured by Nippon Vilene Co., Ltd., 15 g / m 2 ).

[0067] Example 1 An epoxy resin composition was prepared according to the following procedure, and the viscosity, resin flexural modulus, and resin flexural break strain were measured using this composition, and the tackiness of the prepreg was evaluated.

[0068] <Preparation of inorganic particle masterbatch (Step 1)> 30 parts by mass of EPALLOY5000, 6.1 parts by mass of RY200S, and 30 parts by mass of R960 were weighed out, charged into a three-roll mill, and thoroughly mixed to obtain a uniform masterbatch (Masterbatch 1).

[0069] <Preparation of hardener masterbatch (step 2)> 3.6 parts by mass of EPALLOY5000, 3.6 parts by mass of DICY7T, and 2 parts by mass of Omicure24 were weighed out, charged into a three-roll mill, and thoroughly mixed to obtain a uniform masterbatch (masterbatch 2).

[0070] <Preparation of a mixture of component [A] and component [B] (Step 3)> To the masterbatch 1 obtained above, 59.7 parts by mass of EPALLOY5000 and 6.7 parts by mass of PACM were added, and the mixture was heated and mixed at 100 to 150°C to carry out a preliminary reaction, thereby obtaining a mixture (mixture 1) of the constituent element [A] and the constituent element [B].

[0071] <Preparation of epoxy resin composition (step 4)> To 132.5 parts by mass of the mixture 1 obtained above, 15 parts by mass of BX-L was added, and the mixture was heated and mixed at 100 to 150°C to obtain a uniform masterbatch (masterbatch 3).

[0072] This Masterbatch 3 was cooled to 80°C or below, and then the Masterbatch 2 obtained above was added at 80°C or below, and mixed until homogenous to obtain an epoxy resin composition.

[0073] The "Composition before heating" column in Table 1 indicates the amounts of the epoxy resin component and amine component used as raw materials, while the "Composition after heating" column in Table 1 indicates the amounts of the epoxy resin component, amine component, and their pre-reactants in the final composition. Note that in the "Composition after heating" column, "epoxy / amine pre-reactant" indicates a reactant that does not fall under formula (I). The "Composition" column in Table 2 indicates the composition ratio of each component in the final resin composition and the active hydrogen equivalent / epoxy equivalent of the resin composition. To avoid misunderstanding, in the examples described below, a mixture of component [A] and component [B] may not be obtained in step 3.

[0074] [Examples 2 to 12, Comparative Example 3] Resin compositions were obtained in the same manner as in Example 1, except that the amounts of EPALLOY 5000 and PACM added in step 3 were changed, and the type and amount of non-aromatic thermoplastic resin added in step 4 were changed, as shown in Tables 1 and 2. However, for Example 9, a resin composition was obtained by further changing the amounts to use 15 parts by mass of EPALLOY 5000 in step 1, 5.8 parts by mass of EPALLOY 5000 in step 2, and 2.2 parts by mass of EPALLOY 5000 in step 3.

[0075] Comparative Example 4 Resin compositions were obtained in the same manner as in Example 1, except that the amounts of EPALLOY5000 and PACM added in step 3 were changed, and EHPE3150 was further added in step 4, as shown in Tables 1 and 2.

[0076] Comparative Example 5 Resin compositions were obtained in the same manner as in Example 1, except that jER828 was used in place of EPALLOY5000 and the amounts thereof were as shown in Tables 1 and 2.

[0077] [Comparative Example 1] A resin composition was obtained in the same manner as in Example 1, except that step 3 was not performed, and the EPALLOY 5000 that was to be added in step 3 was added in step 1, resulting in the composition ratio of the final composition as shown in Table 2.

[0078] [Examples 14 and 15, Comparative Example 2, and Comparative Examples 6 to 14] A resin composition was obtained in the same manner as in Comparative Example 1, except that the amount of EPALLOY added in step 1 (jER828 was used instead of EPALLOY5000 in Comparative Example 14) was changed, EHPE3150 was further added in step 4, and the type and amount of the non-aromatic thermoplastic resin added in step 4 were changed as shown in Table 2.

[0079] <Method for measuring exothermic peak temperature of epoxy resin composition> An exothermic curve of the epoxy resin composition obtained in the above-mentioned <Preparation of Epoxy Resin Composition> was obtained using a differential scanning calorimeter (DSC Q2500: manufactured by TA Instruments) at a heating rate of 5°C / min in a nitrogen atmosphere. In the obtained exothermic curve, the apex temperature of the exothermic peak having a calorific value of 100 mW / g or more was calculated as the DSC exothermic peak temperature in the present invention. When there were two or more exothermic peaks having a calorific value of 100 mW / g or more, the apex temperature of the peak on the lower side was calculated as the exothermic peak temperature (Table 2, Table 3).

[0080] <Temperature-rise viscosity measurement> The epoxy resin compositions obtained in the above-mentioned <Preparation of Epoxy Resin Composition> were measured for viscosity using a dynamic viscoelasticity analyzer ARES-2KFRTN1-FCO-STD (manufactured by TA Instruments) with flat parallel plates of 25 mm diameter used as upper and lower measuring jigs, with the distance between the upper and lower jigs being 1 mm. The viscosity was then measured in torsion mode (measurement frequency: 0.5 Hz) by increasing the temperature from 20°C to 150°C at a rate of 2°C / min (Tables 2 and 3).

[0081] In Table 2, the viscosities of resin compositions composed of a mixture of components [A] and [B] with a number-average molecular weight in the range of 450 to 800 g / mol were 40,000 Pa·s or more and 200,000 Pa·s or less at 30°C, 300 Pa·s or less at 80°C, and 100 Pa·s or more and 300 Pa·s or less at 100°C (Examples 1 to 7, 10, and 11), except for Example 12, which used a compound with a low number-average molecular weight as component [D].

[0082] On the other hand, the viscosity of resin compositions in which the number average molecular weight of a mixture of component [A] and component [B] was less than 450 g / mol or more than 800 g / mol did not satisfy the above viscosity range at any of 30°C, 80°C, and 100°C (Examples 8 and 9, Comparative Example 1).

[0083] In Examples 13 and 14, the viscosity of the resin composition, which was composed of a component [G] having a number-average molecular weight of 550 to 800 g / mol and a component [D] (component [D']) having a number-average molecular weight in the range of 16,000 to 28,000 g / mol, was 40,000 Pa·s or more and 200,000 Pa·s or less at 30°C, 300 Pa·s or less at 80°C, and 100 Pa·s or more and 300 Pa·s or less at 100°C.

[0084] On the other hand, the viscosities of resin compositions in which the number-average molecular weight of the component [G] was less than 550 g / mol or more than 800 g / mol did not satisfy the above viscosity range at any of 30°C, 80°C, and 100°C (Comparative Examples 6 to 10). The viscosity of the resin composition of Comparative Example 10, in which the number-average molecular weight of the component [D] (component [D']) was less than 16,000 g / mol, was less than 40,000 Pa s at 30°C.

[0085] Furthermore, in resin compositions in which the number average molecular weight of the component [D] (component [D']) exceeded 28,000 g / mol, the bending fracture strain of the cured resin, which will be described later, was lower than that of Example 13 (Comparative Examples 11 to 13).

[0086] <Resin flow evaluation of epoxy resin composition> 3 g of the epoxy resin composition obtained in the above <Preparation of Epoxy Resin Composition> was weighed onto a 15 cm square piece of release film (mass: W4 (g)). The epoxy resin composition was sandwiched between another 15 cm square piece of release film, and then sandwiched between two 10 cm square metal plates (400 g each). The temperature was increased at a rate of 2°C / min and maintained at 180°C for 120 minutes to obtain a cured product. After curing, any excess material protruding from the 10 cm square metal plate was removed, and the mass of the remaining cured product was measured (mass: W5 (g)). The resin flow amount [%] of the epoxy resin composition of the present invention was calculated using the following formula: Resin flow amount = (W4 - W5) / W4 x 100 [%].

[0087] A resin flow rate of 5% or less was designated as A, a rate of more than 5% but not more than 10% as B, and a rate of more than 10% as C (Table 2). Resin compositions with a viscosity of less than 100 Pa s at 100°C were rated as resin flow rates other than A (Examples 8 and 12 and Comparative Examples 1 and 10).

[0088] <Preparation of resin film> The epoxy resin compositions of Examples 1 to 14 and Comparative Examples 1, 2, 5, 7, 8, and 10 to 14 obtained in the above <Preparation of Epoxy Resin Compositions> were heated to 60 to 100°C to form epoxy resin compositions having a basis weight of 80 to 120 g / m. 2The resin compositions of Comparative Examples 6 and 9, which had a viscosity of more than 300 Pa s at 80°C, were hard and had a viscosity of 80 to 120 g / m 2 It was not possible to apply the coating to the release paper within this range (Table 3).

[0089] <Prepreg production> The resin films (surface of the release paper on which the resin film was formed) of Examples 1 to 14 and Comparative Examples 1, 2, 5, 7, 8, and 10 to 14 obtained in the above <Preparation of Resin Film> were impregnated into the glass nonwoven fabric with a pressure sufficient for impregnation.

[0090] <Tackiness evaluation> The prepreg obtained in the above-mentioned <Preparation of Prepreg> was cut into 10 cm square pieces and layered with a 15 cm square FEP film ("Toyoflon (registered trademark)" 50FV, manufactured by Toray Advanced Film Co., Ltd.) on the bottom and the 10 cm square prepreg on the top. A 10 cm square stainless steel plate (400 g) with double-sided adhesive tape attached was placed on top of the layered prepreg and held in place for 30 seconds. The stainless steel plate was then lifted, and when the prepreg peeled off the FEP film and separated into two pieces, if the epoxy resin composition used in the prepreg remained on the FEP film, the tackiness was rated as "poor." If no epoxy resin composition used in the prepreg remained, the tackiness was rated as "good" (Tables 2 and 3).

[0091] In both the Examples and Comparative Examples, the prepregs using resin compositions with a viscosity of 40,000 Pa s or more at 30°C had good tackiness. On the other hand, the prepregs of Comparative Examples 7 and 10, in which the number-average molecular weight of the component [G] was less than 550 g / mol, had poor tackiness.

[0092] <Evaluation of adhesiveness> The prepreg obtained in the above <Prepreg Preparation> was cut into 10 cm square pieces and attached to an aluminum plate of any size (larger than 10 cm square). A 10 cm square stainless steel plate (400 g) that had been sprayed with Daifree GA-3000 (manufactured by Daikin Industries, Ltd.) and treated with a release agent was placed on top of the plate and held for 30 seconds. The stainless steel plate was then lifted, and the aluminum plate was placed at a 90° angle to the ground with the prepreg still attached. If the prepreg was still attached to the aluminum plate after 24 hours, adhesion was evaluated as "good," and if even a portion of the prepreg was removed, adhesion was evaluated as "poor" (Tables 2 and 3). The prepreg prepared using the resin composition of Comparative Example 8, which had a number-average molecular weight of greater than 800 g / mol and a viscosity at 30°C of greater than 200,000 Pa·s, exhibited poor adhesion.

[0093] <Preparation of cured resin board> The epoxy resin composition obtained in the above <Preparation of Epoxy Resin Composition> was degassed in a vacuum, and then sandwiched between stainless steel plates together with a 2 mm thick polytetrafluoroethylene spacer. The temperature was increased at a rate of 2°C / min and maintained at 180°C for 120 minutes to cure the composition, thereby obtaining a cured resin plate.

[0094] <Bending test of cured resin> The 2 mm-thick cured epoxy resin obtained in the above <Preparation of Cured Resin Plate> was cut into a width of 10±0.1 mm and a length of 60±1 mm to obtain a test piece. Three-point bending was performed with a span of 32 mm using an Instron universal testing machine (manufactured by Instron) in accordance with JIS-K7171 (1994), and the elastic modulus and bending strain (elongation) were measured. Six measurements were made, and the average values ​​were calculated (Tables 2 and 3). If the resin plate did not break during the resin bending test, the machine was stopped when the bending deflection exceeded 12 mm, and the strain value at that point was recorded as the breaking strain. In Examples 1 to 12, the bending breaking strain was 4.5% or more. On the other hand, the bending breaking strain of the cured resins of Comparative Examples 1 and 2, which did not contain component [B], was less than 4.5%, failing to meet the target. Furthermore, the greater the amount of component [B] added, the lower the elastic modulus and the larger the bending strain at break. The greater the amount of solid epoxy resin added (component [A]), the higher the elastic modulus and the smaller the bending strain at break. The smaller the amount of component [D] added, the smaller the bending strain at break.

[0095] In both Examples 13 and 14, the bending break strain was 4.5% or more. On the other hand, in Comparative Examples 6 and 8, in which the number-average molecular weight of the constituent element [G] exceeded 800 g / mol, the bending break strain did not reach 4.5%. The bending break strain tended to decrease as the number-average molecular weight of the constituent element [G] increased. Furthermore, the bending break strain of the cured resins of Comparative Examples 11 to 13, in which the number-average molecular weight of the constituent element [D] (constituent element [D']) exceeded 28,000 g / mol, was less than 4.5%, which was not achieved. The bending break strain tended to decrease as the amount of the constituent element [D] added decreased. On the other hand, the modulus of elasticity of the cured resin of Comparative Example 10, in which the number-average molecular weight of the constituent element [D] (constituent element [D']) was less than 16,000 g / mol, was the lowest among the Examples and Comparative Examples.

[0096] <Evaluation of light resistance of cured resin> The 2 mm thick cured epoxy resin material obtained in the above <Preparation of cured resin plate> was cut into a width of 10±0.1 mm and a length of 60±1 mm to obtain a test piece. With half of the surface of the obtained test piece covered with aluminum foil, a metaling weather meter (M6T, manufactured by Suga Test Instruments Co., Ltd.) was used to measure the irradiance at a wavelength of 300 to 400 nm and an illuminance of 1.55 kW / m 2 Furthermore, since it is assumed that the cured product of the epoxy resin composition of the present invention will be exposed to sunlight outdoors for a period of years, the cumulative intensity is set to 1000 kJ / m, which is known as the approximate value of the amount of UV light in one month in Japan (summer). 2 The epoxy resin composition was irradiated with UV light. After irradiation, the aluminum foil was removed, and the appearance of the area covered with the aluminum foil and the area not covered with the foil was visually inspected to see whether or not the cured epoxy resin material had discolored before and after UV irradiation. The color difference of the cured epoxy resin material before and after irradiation was measured using a multi-light source spectrophotometer (MSC-P, manufactured by Suga Test Instruments Co., Ltd.). The epoxy resin composition was placed in the multi-light source spectrophotometer, and the reflectance was measured in the wavelength range of 380 to 780 nm under the following measurement conditions: reflection mode, C light source, 2° field of view, and 8° incidence. Furthermore, the L * a * b * Color measurement value before UV irradiation (L * 1, a * 1, b * Next, the colorimetric value (L * 2, a * 2, b * 2) was measured. Furthermore, the color difference ΔE of the cured product of the epoxy resin composition before and after UV irradiation was measured. * ab ΔE * ab =[(L * 1-L * 2) 2 +(a * 1-a * 2) 2 +(b * 1-b * 2) 2 ] 1 / 2 The calculated ΔE * abIf ΔE is 4 or less, the lightfastness is considered "good" and * ab When the value exceeded 4, the lightfastness was rated as "poor" (Tables 2 and 3).

[0097] Comparative Example 5, which contained 88.5 parts by mass of aromatic epoxy resin, had poor light resistance, indicating that when an aromatic epoxy resin is contained, light resistance tends to be poor.

[0098] Furthermore, Comparative Example 14, which contained 40 parts by mass of aromatic epoxy resin, had poor light resistance, indicating that when an aromatic epoxy resin is contained, light resistance tends to be poor.

[0099] [Table 1]

[0100] [Table 2]

[0101] [Table 3]

Claims

1. An epoxy resin composition comprising components [A], [B], [C], and [D], wherein the non-aromatic epoxy resin of formula (I) in which n is 1 accounts for 95 mass% or more of the total mass of component [B], and the number average molecular weight of the epoxy resin mixture of components [A] and [B] is 450 to 800 g / mol. [A] A non-aromatic epoxy resin other than the component [B] [B] Non-aromatic epoxy resin represented by formula (I) 【Chemistry 1】 Here, R １ is a divalent non-aromatic hydrocarbon group or a group formed by linking non-aromatic hydrocarbon groups via an ether group or an amino group (-NR-, where R is a non-aromatic hydrocarbon group) (hereinafter, "non-aromatic hydrocarbon groups or groups formed by linking non-aromatic hydrocarbon groups via an ether group or an amino group (-NR-, where R is a non-aromatic hydrocarbon group)" are collectively referred to as "non-aromatic organic groups"), and R ２ and R ３ is a non-aromatic organic group in which at least one epoxy group and at least one hydroxyl group have substituted hydrogen atoms of the non-aromatic hydrocarbon group, and R ４ and R ５ is a non-aromatic organic group in which the hydrogen atoms of the non-aromatic hydrocarbon group are substituted with at least one epoxy group and at least one hydroxyl group, a non-aromatic hydrocarbon group that forms part of a nitrogen-containing heterocycle, or a hydrogen atom. １ , R ２ and R ３ is a linear, branched or cyclic structure; R ４ and R ５ is a hydrogen atom, a straight chain, branched or cyclic structure. [C] Curing agent [D] Non-aromatic thermoplastic resin

2. 2. The epoxy resin composition according to claim 1, wherein the number average molecular weight of the component [D] is 16,000 to 28,000 g / mol.

3. 3. The epoxy resin composition according to claim 1 or 2, wherein the component [D] is contained in an amount of 1 to 20 parts by mass when the total of the components [A] and [B] is 100 parts by mass.

4. 3. The epoxy resin composition according to claim 1, wherein component [C] is a non-aromatic curing agent.

5. The epoxy resin composition according to claim 4, wherein the component [C] is dicyandiamide.

6. 3. The epoxy resin composition of claim 1 or 2, further comprising a curing accelerator (component [E]).

7. 3. The epoxy resin composition of claim 1 or 2, further comprising inorganic particles (component "F").

8. 8. The epoxy resin composition according to claim 7, wherein component [F] is a thixotropic agent, and the epoxy resin composition contains 1 to 10 parts by mass of the thixotropic agent when the combined amount of components [A] and [B] is 100 parts by mass.

9. 3. The epoxy resin composition according to claim 1, wherein the viscosity measured at a frequency of 0.5 Hz while increasing the temperature from 20°C to 150°C at a rate of 2°C / min is as follows: 40,000 Pa·s or more and 200,000 Pa·s or less at 30°C 300 Pa·s or less at 80°C 100 Pa·s or more and 300 Pa·s or less at 100°C

10. A prepreg obtained by impregnating a fiber substrate with the epoxy resin composition according to claim 1 or 2.

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