Curable resin composition, and film, molded article, prepreg, and fiber-reinforced plastic using said curable resin composition

Abstract

A curable resin composition including components (A), (B), (C) and (D) below: component (A): a bisphenol epoxy resin with a softening point of 80° C. or more, component (B): a bisphenol epoxy resin which is liquid at 25° C., component (C): a bi- or more-functional (meth)acrylate compound, and component (D): a curing agent.

Claims

1. A prepreg comprising reinforcing fibers and a matrix resin, wherein: the reinforcing fibers are impregnated with the matrix resin, the prepreg is in the form of a sheet, and the matrix resin is a heat-curable resin composition comprising components (A), (B), (C) and (D) below: component (A): a bisphenol epoxy resin with a softening point of 80° C. or more, component (B): a bisphenol epoxy resin which is liquid at 25° C., component (C): a bi- or more-functional (meth)acrylate monomer, and component (D): a curing agent comprising at least one component (d1) selected from the group consisting of a dicyandiamide, a urea, and an imidazole, and at least one component (d2) which is a radical polymerization initiator.

2. The prepreg according to claim 1, which further comprises component (H): an oxazolidone ring-containing epoxy resin.

3. The prepreg according to claim 1, wherein the component (d1) is contained in an amount of 1 to 15 parts by mass with respect to 100 parts by mass of a total of all epoxy resins contained in the heat-curable resin composition.

4. The prepreg according to claim 1, wherein the component (d1) is the dicyandiamide.

5. The prepreg according to claim 1, wherein the component (d1) is the urea.

6. The prepreg according to claim 1, wherein the component (d1) is the imidazole.

7. The prepreg according to claim 1, wherein the component (d2) is contained in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of a total of all epoxy resins and all (meth)acrylate monomers contained in the heat-curable resin composition.

8. The prepreg according to claim 1, wherein the component (A) 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 a total of all epoxy resins contained in the heat-curable resin composition.

9. The prepreg according to claim 1, 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 a total of all epoxy resins contained in the heat-curable resin composition.

10. The prepreg according to claim 1, wherein the component (C) is contained in an amount of 5 to 45 parts by mass with respect to 100 parts by mass of a total of all epoxy resins contained in the heat-curable resin composition.

11. The prepreg according to claim 1, which further comprises component (E): a thermoplastic resin.

12. The prepreg according to claim 11, wherein the component (E) 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 a total of all epoxy resins contained in the heat-curable resin composition.

13. The prepreg according to claim 1, wherein no tri- or more-functional epoxy resins are present in the heat-curable resin composition.

14. The prepreg according to claim 1, wherein the reinforcing fibers comprise a carbon fiber.

Description

EXAMPLES

(1) Hereinbelow, the present invention will be specifically described by way of Examples which should not be construed as limiting the present invention. The raw materials used in the Example and Comparative Examples are shown below.

(2) The softening point and the epoxy equivalent were measured under the following conditions.

(3) 1) Softening point: measured in accordance with JIS-K7234: 2008 (ring and ball method).

(4) 2) Epoxy equivalent: measured in accordance with JIS-K 7236: 2001.

(5) “Raw Materials”

(6) <Component (A)>

(7) jER 1007: Solid bisphenol A epoxy resin (softening point 128° C., manufactured by Mitsubishi Chemical Corporation, product name “jER 1007”).

(8) jER4007P: Solid bisphenol F epoxy resin (softening point: 108° C., manufactured by Mitsubishi Chemical Corporation, product name: “jER4007P”).

(9) jER4004P: Solid bisphenol F epoxy resin (softening point 85° C., manufactured by Mitsubishi Chemical Corporation, product name “jER4004P”).

(10) <Component (B)>

(11) jER 828: Liquid bisphenol A epoxy resin (epoxy equivalent 189 g/eq, manufactured by Mitsubishi Chemical Corporation, product name “jER 828”).

(12) jER 807: Liquid bisphenol F epoxy resin (epoxy equivalent 170 g/eq, manufactured by Mitsubishi Chemical Corporation, product name “jER 807”).

(13) <Component (C)>

(14) Neopentyl glycol diacrylate

(15) Polyethylene glycol #200 dimethacrylate

(16) Trimethylolpropane trimethacrylate

(17) Pentaerythritol tetraacrylate

(18) Dipentaerythritol hexaacrylate

(19) Dioxane glycol diacrylate

(20) Isocyanuric acid EO-modified di- and tri-acrylates

(21) 2-[5-ethyl-5-[(acryloyloxy)methyl]-1,3-dioxane-2-yl]-2,2-dimethylethyl acrylate

(22) Dimethylol-tricyclodecane diacrylate

(23) Pentaerythritol triacrylate toluene diisocyanate urethane prepolymer

(24) Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer

(25) <Component (d1)>

(26) DICY15: dicyandiamide (active hydrogen equivalent 21 g/eq, manufactured by Mitsubishi Chemical Corporation, product name “jER Cure DICY15”).

(27) 1400F: dicyandiamide (active hydrogen equivalent 21 g/eq, manufactured by Air Products and Chemicals, Inc., product name “DICYANEX 1400F”).

(28) DCMU-99: 3-(3,4-dichlorophenyl)-1,1-dimethylurea (Hodogaya Chemical Co., Ltd., trade name “DCMU-99”).

(29) Omicure 94: N,N-dimethyl-N′-phenylurea (manufactured by PTI Japan, Ltd., product name “Omicure 94”).

(30) U-CAT 3513N: isophorone diamine dimethyl urea (manufactured by San-Apro Ltd., product name “U-CAT 3513N”).

(31) Omicure 24: 2,4-bis(3,3-dimethylureido) toluene (manufactured by PT1 Japan, Ltd., product name “Omicure 24”).

(32) <Component (d2)>

(33) Di-t-hexyl peroxide (10-hour half-life temperature 116.4° C.).

(34) Dicumyl peroxide (10-hour half-life temperature 116.4° C.).

(35) <Component (E)>

(36) VINYLEC E: polyvinyl formal resin (manufactured by JNC Corporation, product name “VINYLEC E”).

(37) <Component (H)>

(38) TSR-400: oxazolidone ring-containing epoxy resin (epoxy equivalent 338 g/eq, manufactured by DIC Corporation, product name “TSR-400”).

(39) LSA 3301: oxazolidone ring-containing epoxy resin (epoxy equivalent 403 g/eq, manufactured by Asahi Kasei Corporation, product name “LSA 3301”).

(40) <Carbon Fiber>

(41) TR: manufactured by Mitsubishi Chemical Corporation, product name “PYROFIL TR50S15L”.

(42) MR: manufactured by Mitsubishi Chemical Corporation, product name “PYROFIL MR70 12P”.

Example 1

(43) Using jER4007P as the component (A), jER807 as the component (B), neopentyl glycol diacrylate as the component (C), DICY15 and DCMU-99 as the component (d1), di-t-hexyl peroxide as the component (d2), a curable resin composition was prepared as follows.

(44) First, according to the compositional ratio described in Table 1, the component (B) (liquid) and the component (d1) (solid) were weighed into a container such that the mass ratio of solid component to liquid component became 1:1, followed by addition of a masterbatch containing the component (D). The resulting was stirred to mix the components. The resulting was further finely mixed with a three-roll mill to obtain a curing agent-containing masterbatch.

(45) Subsequently, from the components described in Table 1, the component (A) and the component (B) other than used in the curing agent-containing masterbatch were weighed into a flask, heated to 140° C. using an oil bath, and allowed to be dissolved and mixed. After cooling to about 65° C., the component (C), the curing agent-containing master batch, and the component (d2) were added and stirred to obtain an uncured curable resin composition.

(46) “Production of Resin Plate”

(47) The uncured curable resin composition was poured between two glass plates, molded into a plate, heated at 2° C./min, heat-cured at an oven atmosphere temperature of 135° C. for 90 minutes, to produce a 2 mm-thick resin plate.

(48) “Production of Prepreg”

(49) The uncured curable resin composition was formed into a film by a comma coater (“M-500”, manufactured by Hirano Tecseed Co., Ltd.), and a resin film with a resin coating weight of 16.7 g/m.sup.2 was produced. Thus produced resin films were laminated on both sides of a carbon fiber sheet with a basis weight of 100 g/m.sup.2 obtained by aligning carbon fibers, and the resulting was fed into heating rolls to allow the carbon fiber sheet to be impregnated with the resin, so as to obtain an uncured unidirectional prepreg having a basis weight of 133.4 g/m.sup.2 and a resin content of 25% by mass.

(50) “Production of Fiber-Reinforced Plastic Plate”

(51) The uncured prepreg with a resin content of 25% by mass obtained above was cut into sheets of 300 mm×300 mm, and 24 sheets were laminated such that the relation between the angles of fiber directions of the sheets was [0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°/0°], thereby obtaining a laminate. The laminate was heated in an autoclave at 2° C./min under 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, thereby heat-curing the resin to obtain a fiber-reinforced plastic plate having a thickness of 2.1 mm

(52) “Fabrication of Fiber-Reinforced Plastic Tube”

(53) The fiber-reinforced plastic tube was produced by the method described in (I) to (VI) below.

(54) (I) Two sheets of rectangular prepreg, each having a size of 200 mm in length×72 mm in width, were cut out from the unidirectional prepreg with a resin content of 25% by mass prepared above such that the fiber axis direction was 45° relative to the long side direction. The two sheets pf prepreg were laminated such that the fiber directions of the two sheets intersect each other and one side of each sheet protrudes by 9 mm in the short side direction.

(55) (II) The laminated prepregs obtained above were wound around a release-treated mandrel so that the long side of the laminated prepregs and the axis of the mandrel were aligned in the same direction. The mandrel used was a stainless steel round rod having a diameter of 6 mm and a length of 300 mm.

(56) (III) A rectangular prepreg having a length of 200 mm and a width of 153 mm was cut out from the produced unidirectional prepreg and wound around a mandrel such that the long side direction of the prepreg was aligned with the fiber direction of the prepreg, and the fiber direction was aligned with the mandrel axial direction.

(57) (IV) The resulting was covered by wrapping thereon a heat resistant film tape as a wrapping tape, and was thermoformed in a curing furnace at 130° C. for 90 minutes. The width of the wrapping tape was 15 mm, the tension was 3 N, and the winding pitch (displacement distance in winding) was 1 mm, and this wrapping tape was wrapped so as to have the same thickness as the laminate.

(58) (V) Thereafter, the mandrel was removed and the wrapping tape was removed to obtain a fiber-reinforced plastic tube having an inner diameter of 6 mm and a length of 200 mm.

(59) With respect to the produced resin plate, prepreg and fiber-reinforced plastic, various measurements and evaluations were performed according to the measurement and evaluation methods described below. The results are shown in Table 1.

(60) “Measurement of Flexural Strength, Flexural Modulus, Elongation at Break (Fracture Strain) of Resin Plate”

(61) The resin plate having a thickness of 2 mm obtained in the section “Production of Resin Plate” was processed into a test piece of 60 mm in length×8 mm in width. With respect to the test piece, the flexural strength, flexural modulus and elongation at break (fracture strain) of the resin plate were measured using a universal tester (“INSTRON 5565”, manufactured by INSTRON) equipped with a 3-point bending jig (indenter R=3.2 mm, support R=3.2 mm, distance between supports (L)=32 mm) at a temperature of 23° C. under a humidity of 50% RH with a crosshead speed of 2 mm/min.

(62) “Measurement of 0° Flexural Strength/Flexural Modulus, and 90 Flexural Strength/Flexural Modulus of Fiber-Reinforced Plastic Plate”

(63) The fiber-reinforced plastic plate having a thickness of 2.1 mm produced in the section “Preparation of Fiber-Reinforced Plastic Plate” was processed into a test piece of 60 mm in length×12.7 mm in width. With respect to the test piece, the flexural properties of the fiber-reinforced plastic plate in terms of 0° flexural strength/flexural modulus, and 90° flexural strength/flexural modulus were measured using a universal tester (“INSTRON 5565”, manufactured by INSTRON) equipped with a 3-point bending jig (indenter R=5.0 mm, support R=3.2 mm) with L/d=16 (L is a distance between supports and d is a thickness of the test piece) and a crosshead speed (per minute) of (L2×0.01)/(6×d).

(64) “Measurement of Flexural Strength, Flexural Modulus and Strain at Maximum Load of Fiber-Reinforced Plastic Tube”

(65) With respect to the fiber-reinforced plastic tube having an inner diameter of 6 mm and a length of 200 mm, which was obtained in the section “Fabrication of Fiber-Reinforced Plastic Tube”, the flexural properties of the fiber-reinforced plastic tube in terms of flexural strength, flexural modulus and strain at maximum load were measured using a universal tester (“INSTRON 5565”, manufactured by INSTRON) equipped with a 3-point bending jig (indenter R=75 mm, support R=12.5 mm, distance between supports (L)=150 mm) with a crosshead speed of 20 mm/min.

Examples 2 to 24, Comparative Example 1

(66) Curable resin compositions were prepared in the same manner as in Example 1 except that the compositional ratios were changed to those shown in Tables 1 and 2, and resin plates, prepregs, fiber-reinforced plastic plates, fiber-reinforced plastic tubes were produced, on which various measurements and evaluations were performed. The evaluation results are shown in Table 1 and Table 2. (In Tables 1 and 2, each of the amounts of the component (A) and the component (B) is an amount (parts by mass) with respect to 100 parts by mass of total of all epoxy resins, the amount of the component (d2) is an amount (part by mass) with respect to 100 parts by mass of total of all epoxy resins and all (meth)acrylate compounds contained in the curable resin composition, and the amount of other components is an amount (part by mass) with respect to 100 parts by mass of total of all epoxy resins.)

(67) TABLE-US-00001 TABLE 1 Example Composition (part by mass) 1 2 3 4 5 6 7 Component (A) jER1007 0 0 0 0 50 0 0 jER4007P 50 50 50 50 0 50 50 Component (B) jER828 0 0 0 0 50 0 0 jER807 50 50 50 50 0 50 50 Component (C) Neopentyl glycol diacrylate 25 0 0 0 0 0 0 Polyethylene glycol # 200 0 25 0 0 0 0 0 dimethacrylate Trimethylolpropane triacrylate 0 0 0 0 0 0 0 Trimethylolpropane trimethacrylate 0 0 25 0 0 0 0 Pentaerythritol tetraacrylate 0 25 0 25 25 0 0 Dipentaerythritol hexaacrylate 0 0 0 0 0 25 5 Isocyanuric acid EO-modified di- 0 0 0 0 0 0 0 and tri-acrylates 2-[5-ethyl-5-[(acryloyloxy)methyl]- 0 0 0 0 0 0 0 1,3-dioxane-2-yl]-2,2- dimethylethyl acrylate Dimethylol-tricyclodecane diacrylate 0 0 0 0 0 0 0 Pentaerythritol triacrylate toluene 0 0 0 0 0 0 0 diisocyanate urethane prepolymer Pentaerythritol triacrylate hexamethylene 0 0 0 0 0 0 0 diisocyanate urethane prepolymer Component (D) (d1) DICY15 4.4 4.4 4.4 4.4 4 4.4 4.4 1400F 0 0 0 0 0 0 0 DCMU-99 3 3 3 3 3 3 3 Omicure94 0 0 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.6 0.5 0.7 0.8 0.8 0.8 0.2 Component (E) VINYLEC E 0 0 0 0 0 0 0 Physical Properties of Resin Plate Flexural Strength [MPa] 177 164 182 179 170 174 166 Flexural Modulus [GPa] 3.95 3.79 4.09 4.11 3.8 3.96 3.73 Elongation at Break [%] 12.8 13.9 7.4 10.2 11.4 10.1 13.7 Example Composition (part by mass) 8 9 10 11 12 13 Component (A) jER1007 0 0 0 0 0 0 jER4007P 50 50 50 50 50 50 Component (B) jER828 0 0 0 0 0 0 jER807 50 50 50 50 50 50 Component (C) Neopentyl glycol diacrylate 0 0 0 0 0 0 Polyethylene glycol # 200 0 0 0 0 0 0 dimethacrylate Trimethylolpropane triacrylate 0 0 0 0 0 0 Trimethylolpropane trimethacrylate 0 0 0 0 0 0 Pentaerythritol tetraacrylate 0 0 0 0 0 0 Dipentaerythritol hexaacrylate 5 15 15 35 35 45 Isocyanuric acid EO-modified di- 0 0 0 0 0 0 and tri-acrylates 2-[5-ethyl-5-[(acryloyloxy)methyl]- 0 0 0 0 0 0 1,3-dioxane-2-yl]-2,2- dimethylethyl acrylate Dimethylol-tricyclodecane diacrylate 0 0 0 0 0 0 Pentaerythritol triacrylate toluene 0 0 0 0 0 0 diisocyanate urethane prepolymer Pentaerythritol triacrylate hexamethylene 0 0 0 0 0 0 diisocyanate urethane prepolymer Component (D) (d1) DICY15 4.4 4.4 4.4 4.4 4.4 4.4 1400F 0 0 0 0 0 0 DCMU-99 3 3 3 3 3 3 Omicure94 0 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.7 0.5 0.8 0.9 1.1 1.0 Component (E) VINYLEC E 0 0 0 0 0 0 Physical Properties of Resin Plate Flexural Strength [MPa] 165 171 167 177 177 176 Flexural Modulus [GPa] 4.07 3.84 3.83 4.39 3.96 4.29 Elongation at Break [%] 14.1 13.5 10.9 7.7 11.9 8.4

(68) TABLE-US-00002 TABLE 2 Example Composition (part by mass) 14 15 16 17 18 19 20 Component (A) jER1007 0 0 0 0 0 0 0 jER4007P 50 50 50 50 50 50 50 Component (B) jER828 0 0 0 0 0 0 0 jER807 50 50 50 50 50 50 50 Component (C) Neopentyl glycol diacrylate 0 0 0 0 0 0 0 Polyethylene glycol # 200 0 0 0 0 0 0 0 dimethacrylate Trimethylolpropane triacrylate 0 0 0 0 0 0 0 Trimethylolpropane trimethacrylate 0 0 0 0 0 0 0 Pentaerythritol tetraacrylate 0 0 0 0 0 0 0 Dipentaerythritol hexaacrylate 45 25 25 25 25 25 0 Isocyanuric acid EO-modified di- 0 0 0 0 0 0 25 and tri-acrylates 2-[5-ethyl-5-[(acryloyloxy)methyl]- 0 0 0 0 0 0 0 1,3-dioxane-2-yl]-2,2- dimethylethyl acrylate Dimethylol-tricyclodecane diacrylate 0 0 0 0 0 0 0 Pentaerythritol triacrylate toluene 0 0 0 0 0 0 0 diisocyanate urethane prepolymer Pentaerythritol triacrylate hexamethylene 0 0 0 0 0 0 0 diisocyanate urethane prepolymer Component (D) (d1) DICY15 4.4 0 0 4.4 4.4 0 4.4 1400F 0 4.4 3.8 0 0 4.4 0 DCMU-99 3 3 3 3 3 0 3 Omicure94 0 0 0 0 0 2 0 (d2) Di-t-hexyl peroxide 1.4 0.8 0.8 0.8 0.8 0.8 0.8 Component (E) VINYLEC E 0 0 0 3 5 0 0 Physical Properties of Resin Plate Flexural Strength [MPa] 174 180 179 172 169 170 178 Flexural Modulus [GPa] 3.80 4.23 4.17 4.12 4.02 3.81 4.07 Elongation at Break [%] 9.1 10.2 9.2 10.8 11.98 13.0 12.5 Comparative Example Example Composition (part by mass) 21 22 23 24 1 Component (A) jER1007 0 0 0 0 50 jER4007P 50 50 50 50 0 Component (B) jER828 0 0 0 0 50 jER807 50 50 50 50 0 Component (C) Neopentyl glycol diacrylate 0 0 0 0 0 Polyethylene glycol # 200 0 0 0 0 0 dimethacrylate Trimethylolpropane triacrylate 0 0 0 0 0 Trimethylolpropane trimethacrylate 0 0 0 0 0 Pentaerythritol tetraacrylate 0 0 0 0 0 Dipentaerythritol hexaacrylate 0 0 0 0 0 Isocyanuric acid EO-modified di- 0 0 0 0 0 and tri-acrylates 2-[5-ethyl-5-[(acryloyloxy)methyl]- 25 0 0 0 0 1,3-dioxane-2-yl]-2,2- dimethylethyl acrylate Dimethylol-tricyclodecane diacrylate 0 25 0 0 0 Pentaerythritol triacrylate toluene 0 0 25 0 0 diisocyanate urethane prepolymer Pentaerythritol triacrylate hexamethylene 0 0 0 25 0 diisocyanate urethane prepolymer Component (D) (d1) DICY15 4.4 4.4 4.4 4.4 4 1400F 0 0 0 0 0 DCMU-99 3 3 3 3 3 Omicure94 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.8 0.8 0.8 0.8 0 Component (E) VINYLEC E 0 0 0 0 0 Physical Properties of Resin Plate Flexural Strength [MPa] 169 166 173 173 142 Flexural Modulus [GPa] 4.0 3.94 4.02 3.96 3.15 Elongation at Break [%] 12.6 13.9 10.6 9.7 10.3

(69) As shown in Tables 1 and 2, each of the Example was superior to Comparative Example 1 without the component (C) in that the resin plate was excellent in strength and elastic modulus, while maintaining toughness. Moreover, the physical properties of the fiber-reinforced plastic plate and the fiber-reinforced plastic tube were improved in each of the Examples as compared to Comparative Example 1 without the component (C).

Example 25

(70) Using jER4007P as the component (A), jER807 as the component (B), neopentyl glycol diacrylate as the component (C), DICY15 and DCMU-99 as the component (d1), di-t-hexyl peroxide as the component (d2), and TSR-400 as the component (E), a curable resin composition was prepared as follows.

(71) First, according to the compositional ratio described in Table 1, the component (B) (liquid) and the component (d1) (solid) were weighed into a container such that the mass ratio of solid component to liquid component became 1:1, followed by addition of a masterbatch containing the component (D). The resulting was stirred to mix the components. The resulting was further finely mixed with a three-roll mill to obtain a curing agent-containing masterbatch.

(72) Subsequently, from the components described in Table 1, the component (A), the component (B) other than used in the curing agent-containing masterbatch and the component (H) were weighed into a flask, heated to 140° C. using an oil bath, and allowed to be dissolved and mixed. After cooling to about 65° C., the component (C), the curing agent-containing master batch, and the component (d2) were added and stirred to obtain an uncured curable resin composition.

(73) The various measurements and evaluations were performed with respect to the resin plate, prepreg and fiber-reinforced plastic produced using the obtained uncured curable resin composition. The results are shown in Table 3.

Examples 26 to 52, Comparative Examples 2 and 3

(74) Curable resin compositions were prepared in the same manner as in Example 25 except that the compositional ratios were changed to those shown in Tables 1 and 2, and resin plates, prepregs, fiber-reinforced plastic plates, fiber-reinforced plastic tubes were produced, on which various measurements and evaluations were performed. The evaluation results are shown in Table 3 and Table 4. (In Tables 3 and 4, each of the amounts of the component (A), the component (B) and the component (H) is an amount (parts by mass) with respect to 100 parts by mass of total of all epoxy resins, the amount of the component (d2) is an amount (part by mass) with respect to 100 parts by mass of total of all epoxy resins and all (meth)acrylate compounds contained in the curable resin composition, and the amount of other components is an amount (part by mass) with respect to 100 parts by mass of total of all epoxy resins.)

(75) TABLE-US-00003 TABLE 3 Example Composition (part by mass) 25 26 27 28 29 30 31 32 Component (A) jER4007P 20 20 20 20 20 20 20 20 Component (B) jER807 50 50 50 50 50 50 50 50 Component (H) TSR-400 30 30 30 30 30 30 30 30 LSA3301 0 0 0 0 0 0 0 0 Component (C) Neopentyl glycol diacrylate 25 0 0 0 0 0 0 0 Trimethylolpropane triacrylate 0 25 0 0 0 0 0 0 Pentaerythritol tetraacrylate 0 0 25 0 0 0 0 0 Dipentaerythritol hexaacrylate 0 0 0 25 0 0 0 0 Dioxane glycol diacrylate 0 0 0 0 25 0 0 0 Dimethylol-tricyclodecane diacrylate 0 0 0 0 0 25 0 0 Pentaerythritol triacrylate toluene 0 0 0 0 0 0 25 0 diisocyanate urethane prepolymer Pentaerythritol triacrylate hexamethylene 0 0 0 0 0 0 0 25 diisocyanate urethane prepolymer Component (D) (d1) 1400F 5.4 5.4 5.4 5.4 5.4 5.4 5.4 5.4 DCMU-99 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 Omicure94 0 0 0 0 0 0 0 0 U-CAT 3513N 0 0 0 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Component (E) VINYLEC E 0 0 0 0 0 0 0 0 Flexural Properties Flexural Strength [MPa] 174 171 182 187 175 179 184 182 of Resin Plate Flexural Modulus [GPa] 3.8 3.7 3.9 4.0 3.9 4.0 4.0 3.9 Elongation at Break [%] 9 9 9 11 12 11 8 8 Fiber- TR Strength [MPa] — — — — — — — — Reinforced Flexural Modulus [GPa] — — — — — — — — Plastic Tube Fracture Strain [%] — — — — — — — — MR Strength [MPa] — — — — — — — — Flexural Modulus [GPa] — — — — — — — — Fracture Strain [%] — — — — — — — — Example Composition (part by mass) 33 34 35 36 37 38 39 Component (A) jER4007P 20 20 30 50 50 50 20 Component (B) jER807 50 50 60 40 40 40 60 Component (H) TSR-400 30 30 10 10 10 10 20 LSA3301 0 0 0 0 0 0 0 Component (C) Neopentyl glycol diacrylate 0 0 0 0 0 0 0 Trimethylolpropane triacrylate 0 0 0 0 0 0 0 Pentaerythritol tetraacrylate 0 0 0 0 0 0 0 Dipentaerythritol hexaacrylate 25 25 25 25 25 25 25 Dioxane glycol diacrylate 0 0 0 0 0 0 0 Dimethylol-tricyclodecane diacrylate 0 0 0 0 0 0 0 Pentaerythritol triacrylate toluene 0 0 0 0 0 0 0 diisocyanate urethane prepolymer Pentaerythritol triacrylate hexamethylene 0 0 0 0 0 0 0 diisocyanate urethane prepolymer Component (D) (d1) 1400F 5.4 5.4 5.5 4 4 4 5.8 DCMU-99 0 0 3.7 2.7 2.7 2.7 3.9 Omicure94 2.6 0 0 0 0 0 0 U-CAT 3513N 0 2.4 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.8 0.8 0.8 0.4 0.8 2 0.8 Component (E) VINYLEC E 0 0 0 0 0 0 0 Flexural Properties Flexural Strength [MPa] 190 185 186 172 180 177 187 of Resin Plate Flexural Modulus [GPa] 4.0 3.9 4.2 4.0 4.1 4.1 4.1 Elongation at Break [%] 8 9 9 9 9 8 8 Fiber- TR Strength [MPa] — — — — 1835 — — Reinforced Flexural Modulus [GPa] — — — — 68 — — Plastic Tube Fracture Strain [%] — — — — 11 — — MR Strength [MPa] — — — — 2063 — — Flexural Modulus [GPa] — — — — 90 — — Fracture Strain [%] — — — — 9 — —

(76) TABLE-US-00004 TABLE 4 Example Composition (part by mass) 40 41 42 43 44 45 46 47 Component (A) jER4007P 40 30 10 30 30 30 30 30 Component (B) jER807 40 40 60 40 40 40 40 40 Component (H) TSR-400 20 30 30 30 30 30 30 0 LSA3301 0 0 0 0 0 0 0 30 Component (C) Neopentyl glycol diacrylate 0 0 0 0 0 0 0 0 Trimethylolpropane triacrylate 0 0 0 0 0 0 0 0 Pentaerythritol tetraacrylate 0 0 0 0 0 0 0 0 Dipentaerythritol hexaacrylate 25 25 25 25 25 25 25 25 Dioxane glycol diacrylate 0 0 0 0 0 0 0 0 Dimethylol-tricyclodecane diacrylate 0 0 0 0 0 0 0 0 Pentaerythritol triacrylate toluene 0 0 0 0 0 0 0 0 diisocyanate urethane prepolymer Pentaerythritol triacrylate 0 0 0 0 0 0 0 0 hexamethylene diisocyanate urethane prepolymer Component (D) (d1) 1400F 4.3 4.7 6.2 4.7 4.7 4.7 4.7 4.5 DCMU-99 2.9 3.2 4.2 3.2 3.2 3.2 3.2 2.9 Omicure94 0 0 0 0 0 0 0 0 U-CAT 3513N 0 0 0 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.8 0.4 0.8 2 0.8 0.8 0.8 0.8 Component (E) VINYLEC E 0 0 0 0 0 1 3 1 Flexural Properties Flexural Strength [MPa] 179 176 186 181 186 180 179 182 of Resin Plate Flexural Modulus [GPa] 4.0 3.9 3.9 4.0 4.0 3.9 3.9 4.0 Elongation at Break [%] 10 8 9 8 12 8 9 8 Fiber- TR Strength [MPa] — — — — 2051 — — — Reinforced Flexural Modulus [GPa] — — — — 71 — — — Plastic Tube Fracture Strain [%] — — — — 11 — — — MR Strength [MPa] — — — — 2081 — — — Flexural Modulus [GPa] — — — — 91 — — — Fracture Strain [%] — — — — 9 — — — Example Comp. Ex. Composition (part by mass) 48 49 50 51 52 2 3 Component (A) jER4007P 40 10 30 10 30 50 30 Component (B) jER807 30 50 30 40 20 40 40 Component (H) TSR-400 30 40 40 50 50 10 30 LSA3301 0 0 0 0 0 0 0 Component (C) Neopentyl glycol diacrylate 0 0 0 0 0 0 0 Trimethylolpropane triacrylate 0 0 0 0 0 0 0 Pentaerythritol tetraacrylate 0 0 0 0 0 0 0 Dipentaerythritol hexaacrylate 25 25 25 25 25 0 0 Dioxane glycol diacrylate 0 0 0 0 0 0 0 Dimethylol-tricyclodecane diacrylate 0 0 0 0 0 0 0 Pentaerythritol triacrylate toluene 0 0 0 0 0 0 0 diisocyanate urethane prepolymer Pentaerythritol triacrylate 0 0 0 0 0 0 0 hexamethylene diisocyanate urethane prepolymer Component (D) (d1) 1400F 3.9 5.8 4.3 5.4 3.9 4 4.7 DCMU-99 2.7 3.9 2.9 3.6 2.6 2.7 3.2 Omicure94 0 0 0 0 0 0 0 U-CAT 3513N 0 0 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.8 0.8 0.8 0.8 0.8 0 0 Component (E) VINYLEC E 0 0 0 0 0 0 0 Flexural Properties Flexural Strength [MPa] 178 185 180 182 181 155 160 of Resin Plate Flexural Modulus [GPa] 4.1 4.1 3.9 3.9 3.9 3.8 3.8 Elongation at Break [%] 9 8 9 8 8 14 14 Fiber- TR Strength [MPa] — — — — — 1830 1883 Reinforced Flexural Modulus [GPa] — — — — — 63 68 Plastic Tube Fracture Strain [%] — — — — — 11 11 MR Strength [MPa] — — — — — 1813 2080 Flexural Modulus [GPa] — — — — — 82 89 Fracture Strain [%] — — — — — 8 9

(77) As shown in Tables 3 and 4, each of the Example was superior to Comparative Examples 1 and 2 without the component (C) in that the resin plate was excellent in strength and elastic modulus, while maintaining toughness. Moreover, the physical properties of the fiber-reinforced plastic tube were improved in each of the Examples as compared to Comparative Example 1 without the component (C).

Examples 53 to 57, Comparative Examples 4 to 6

(78) Curable resin compositions were prepared in the same manner as in Example 1 except that the compositional ratios were changed to those shown in Table 5, and resin plates, prepregs, fiber-reinforced plastic plates, fiber-reinforced plastic tubes were produced, on which various measurements and evaluations were performed. The evaluation results are shown in Table 5.

(79) TABLE-US-00005 TABLE 5 Comp. Comp. Comp. Composition (part by mass) Ex. 53 Ex. 54 Ex. 55 Ex. 56 Ex. 57 Ex. 58 Ex. 59 Ex. 4 Ex. 5 Ex. 6 Component(A) jER4004P 50 0 0 0 0 0 0 0 0 0 jER4007P 0 50 50 50 50 22 22 0 0 0 Epoxy resin jER1001 0 0 0 0 0 0 0 50 50 0 other than jER1002 0 0 0 0 0 0 0 0 0 50 Component(A) Component(B) jER828 0 0 0 0 0 0 0 50 50 50 jER807 50 50 50 50 50 28 28 0 0 0 Component(H) TSR-400 0 0 0 0 0 50 50 0 0 0 Component(C) Dipentaerythritol hexaacrylate 25 25 25 25 25 25 25 0 25 25 Component (D) (d1) 1400F 4.8 4.4 4.4 2.7 5.3 4.5 4.5 5.2 5.2 4.8 DCMU-99 3.2 0 1 3 3 2.9 2.9 3.5 3.5 3.2 Omicure24 0 1.7 0 0 0 0 0 0 0 0 (d2) Di-t-hexyl peroxide 0.8 0.8 0.8 0.8 0.8 0 0 0 0.8 0.8 Dicumyl peroxide 0 0 0 0 0 0.4 0.8 0 0 0 Component(E) VINYLEC E 0 0 0 0 0 3 3 0 0 0 Flexural Properties Flexural Strength [MPa] 173 178 177 170 174 182 185 150 166 160 of Resin Plate Flexural Modulus [GPa] 3.9 3.8 3.9 3.7 3.7 3.8 4 3.3 3.3 3.5 Elongation at Break [%] 10 7 7 9 8 8 9 14 9 14

INDUSTRIAL APPLICABILITY

(80) The use of the curable resin composition of the present invention enables production of an excellent fiber-reinforced plastic tube. Therefore, the present invention can provide wide variety of fiber-reinforced plastic molded articles with excellent mechanical properties, ranging from, for example, molded articles for sports and leisure applications such as golf club shafts, to molded articles for industrial applications such as aircrafts.