Fiber-reinforced epoxy resin material, prepreg and, tubular body made of fiber-reinforced epoxy resin material

Patent metadata

Field	Value
Publication number	US-9840058-B2
Application number	US-201314439582-A
Country	US
Kind code	B2
Filing date	Oct 31, 2013
Priority date	Oct 31, 2012
Publication date	Dec 12, 2017
Grant date	Dec 12, 2017

Abstract

An object of the present invention is to provide a novel fiber-reinforced epoxy resin material having improved strength. The fiber-reinforced epoxy resin material of the present invention comprises a cured product of an epoxy resin composition and a reinforcing fiber, wherein the epoxy resin composition comprises a novolac type epoxy resin as an epoxy resin component, and the cured product of the epoxy resin composition has a swelling ratio in a range from 20 mass % to 44 mass % in methyl ethyl ketone.

First claim

The invention claimed is:

1. A fiber-reinforced epoxy resin material comprising a cured product of an epoxy resin composition and a reinforcing fiber,
wherein the epoxy resin composition comprises an epoxy resin component including a novolac type epoxy resin, and a thermoplastic resin,
the novolac type epoxy resin content in the epoxy resin component ranges from 2 mass % to 10 mass %,
the thermoplastic resin is present in an amount ranging from 2 parts by mass to 12 parts by mass with respect to 100 parts by mass of the epoxy resin component, and

the cured product of the epoxy resin composition has a swelling ratio in a range from 20 mass % to 44 mass % in methyl ethyl ketone at 40° C. for 48 hours.

2. The fiber-reinforced epoxy resin material according to claim 1 , wherein the epoxy resin composition comprises a polyvinyl formal as the thermoplastic resin.

3. The fiber-reinforced epoxy resin material according to claim 1 , wherein the epoxy resin composition comprises dicyandiamide as a curing agent and a urea derivative as a curing accelerator.

4. The fiber-reinforced epoxy resin material according to claim 1 , wherein the epoxy resin composition comprises dicyandiamide as a curing agent in an amount ranging from 13 g to 40 g with respect to 1 mole of an epoxy group of the epoxy resin component.

5. The fiber-reinforced epoxy resin material according to claim 1 , wherein the epoxy resin component comprises the novolac type epoxy resin and a phenoxy type epoxy resin.

6. The fiber-reinforced epoxy resin material according to claim 5 , wherein a mass ratio of the novolac type epoxy resin to the phenoxy type epoxy resin (novolac type epoxy resin/phenoxy type epoxy resin) in the epoxy resin component ranges from 0.4 to 7.

7. The fiber-reinforced epoxy resin material according to claim 5 , wherein the epoxy resin component further comprises a bisphenol A type epoxy resin and a bisphenol F type epoxy resin.

8. The fiber-reinforced epoxy resin material according to claim 5 , wherein a weight average molecular weight of the phenoxy type epoxy resin is 1,000 or more and 130,000 or less.

9. The fiber-reinforced epoxy resin material according to claim 5 , wherein an epoxy equivalent (g/eq) of the phenoxy type epoxy resin is 4,000 or more and 20,000 or less.

10. The fiber-reinforced epoxy resin material according to claim 1 , wherein a content of the reinforcing fiber in the fiber-reinforced epoxy resin material ranges from 65 mass % to 85 mass %.

11. The fiber-reinforced epoxy resin material according to claim 1 , wherein the reinforcing fiber includes a carbon fiber.

12. The fiber-reinforced epoxy resin material according to claim 1 , wherein the reinforcing fiber has a tensile modulus ranging from 10 tf/mm 2 to 70 tf/mm 2 .

13. A prepreg used for preparing a fiber-reinforced epoxy resin material,
wherein the prepreg comprises an epoxy resin composition and a reinforcing fiber,
the epoxy resin composition comprises an epoxy resin component including a novolac type epoxy resin, and a thermoplastic resin,
the novolac type epoxy resin content in the epoxy resin component ranges from 2 mass % to 10 mass %,
the thermoplastic resin is present in an amount ranging from 2 parts by mass to 12 parts by mass with respect to 100 parts by mass of the epoxy resin component, and
a cured product of the epoxy resin composition has a swelling ratio in a range from 20 mass % to 44 mass % in methyl ethyl ketone at 40° C. for 48 hours.

14. The prepreg according to claim 13 , wherein the epoxy resin component comprises the novolac type epoxy resin and a phenoxy type epoxy resin.

15. A tubular body made of a fiber-reinforced epoxy resin material, wherein the fiber-reinforced epoxy resin material comprises a cured product of an epoxy resin composition and a reinforcing fiber,
the epoxy resin composition comprises an epoxy resin component including a novolac type epoxy resin, and a thermoplastic resin,
the novolac type epoxy resin content in the epoxy resin component ranges from 2 mass % to 10 mass %,
the thermoplastic resin is present in an amount ranging from 2 parts by mass to 12 parts by mass with respect to 100 parts by mass of the epoxy resin component, and
the cured product of the epoxy resin composition has a swelling ratio in a range from 20 mass % to 44 mass % in methyl ethyl ketone at 40° C. for 48 hours.

16. A tubular body made of a fiber-reinforced epoxy resin material, wherein the tubular body is obtained by laminating multiple prepregs and curing a resin composition comprised in the prepregs;
the outermost prepreg locating on the outermost side is a prepreg comprising an epoxy resin composition and a reinforcing fiber, in which the epoxy resin composition comprises an epoxy resin component including a novolac type epoxy resin, and a thermoplastic resin,
the novolac type epoxy resin content in the epoxy resin component ranges from 2 mass % to 10 mass %,
the thermoplastic resin is present in an amount ranging from 2 parts by mass to 12 parts by mass with respect to 100 parts by mass of the epoxy resin component, and
a cured product of the epoxy resin composition has a swelling ratio in a range from 20 mass % to 44 mass % in methyl ethyl ketone at 40° C. for 48 hours; and
at least one of the prepregs locating on the inner side of the outermost prepreg has a smaller density than the outermost prepreg.

17. The tubular body made of the fiber-reinforced epoxy resin material according to claim 16 , wherein the reinforcing fiber comprised in the prepreg which has a smaller density than the outermost prepreg has a larger tensile modulus than the reinforcing fiber comprised in the outermost prepreg.

18. The tubular body made of the fiber-reinforced epoxy resin material according to claim 16 , wherein the reinforcing fiber comprised in the outermost prepreg has a tensile modulus ranging from 10 tf/mm 2 to 38 tf/mm 2 , and the reinforcing fiber comprised in the prepreg which has a smaller density than the outermost prepreg has a tensile modulus ranging from 30 tf/mm 2 to 70 tf/mm 2 .

19. A golf club shaft comprising a tubular body made of a fiber-reinforced epoxy resin material, wherein the fiber-reinforced epoxy resin material comprises a cured product of an epoxy resin composition and a reinforcing fiber,
the epoxy resin composition comprises an epoxy resin component including a novolac type epoxy resin, and a thermoplastic resin,
the novolac type epoxy resin content in the epoxy resin component ranges from 2 mass % to 10 mass %,
the thermoplastic resin is present in an amount ranging from 2 parts by mass to 12 parts by mass with respect to 100 parts by mass of the epoxy resin component, and

the cured product of the epoxy resin composition has a swelling ratio in a range from 20 mass % to 44 mass % in methyl ethyl ketone at 40° C. for 48 hours.

Assignees

• Dunlop Sports Co Ltd
• Dunlop Sports Co Ltd

Inventors

• Tsunashima Hiromasa
• Naito Yasuo
• Shiga Kazuyoshi

Classifications

• A63B49/10

  made of non-metallic materials, other than wood · CPC title

• C08J5/24

  Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs · CPC title

• A63B2209/02

  with reinforcing fibres, e.g. carbon, polyamide fibres · CPC title

• B32B2260/023

  Two or more layers · CPC title

• C08J2463/02

  Polyglycidyl ethers of bis-phenols · CPC title