Epoxy resin composition, prepreg, and carbon fiber-reinforced composite material

Patent metadata

Field	Value
Publication number	US-10400076-B2
Application number	US-201414896865-A
Country	US
Kind code	B2
Filing date	Jul 10, 2014
Priority date	Jul 11, 2013
Publication date	Sep 3, 2019
Grant date	Sep 3, 2019

Abstract

An epoxy resin composition including [A1] a hardener represented by Formula (1), and [B] an aromatic epoxy resin having tri- or higher functionality, wherein a carbon nuclear relaxation time T 1 C corresponding to a benzene ring carbon atom in the main backbone of Formula (1) assigned to 130 ppm in a solid-state 13 C-NMR spectrum is 42 seconds or longer, and a prepreg and a carbon fiber-reinforced composite material obtained using the epoxy resin composition:

wherein X represents any one selected from —CH 2 —, —O—, —CO—, —C(═O)O—, —S—, —SO 2 —, and —NHC(═O)—; n represents 1 to 5; and R 1 to R 6 each represent at least one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 4 or less carbon atoms, and an a halogen atom, wherein when X is —C(═O)O— or —NHC(═O)—, X may be in either direction.

Provided are an epoxy resin composition that provides a carbon fiber-reinforced composite material excellent in tensile strength and compression strength and suitable as a structural material, a prepreg, and a carbon fiber-reinforced composite material.

First claim

The invention claimed is:

1. An epoxy resin composition comprising
[A1] hardener particles having an average particle size of less than 20 μm and represented by Formula (1)

wherein X represents —NHC(═O)—; n represents 1; and R 1 to R 6 each represent a hydrogen atom, wherein X may be in either direction; and
an epoxy resin component comprising at least 40% by weight of [B]; and a balance of [C] and/or a bisphenol-type epoxy resin;
[B] a tetraglycidyl aromatic epoxy resin represented by Formula (8)

wherein T is —NHC(═O)—; n represents 0 to 5; and R 1 to R 6 each represent at least one selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 4 or less carbon atoms, and a halogen atom, wherein T may be in either direction; and
[C] an epoxy resin having at least one ring structure having a 4- or more membered ring and one or two amine type glycidyl groups or ether type glycidyl groups directly connected to the ring structure;
wherein the equivalent ratio of all active hydrogens of amino groups in the component [A1] to all epoxy groups in the epoxy resin composition is 0.4 to 1.0, and the equivalent ratio of all active hydrogens of amino groups in the epoxy resin composition to all epoxy groups in the epoxy resin composition does not exceed 1.0;
wherein the epoxy resin composition has a curing calorific value of less than 450 J/g, as determined by differential scanning calorimetry (DSC) at a temperature ramp rate of 5° C./min; and
wherein a cured product of the epoxy resin composition has a carbon nuclear relaxation time T 1 C corresponding to a benzene ring carbon atom in the main backbone of Formula (1) assigned to 130 ppm in a solid-state 13 C-NMR spectrum of 42 seconds or longer.

2. The epoxy resin composition according to claim 1 , wherein the carbon nuclear relaxation time T 1 C corresponding to a benzene ring carbon atom in the main backbone of Formula (1) assigned to 130 ppm in a solid-state 13 C-NMR spectrum is 48 seconds or longer.

3. The epoxy resin composition according to claim 1 , wherein the component [A1] is a hardener having a structure represented by Formula (2) or Formula (3):

4. The epoxy resin composition according to claim 1 , wherein the component [C] comprises an epoxy resin having a structure represented by Formula (9):

wherein
R 1 and R 2 each represent at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, an acyl group, a trifluoromethyl group, and a nitro group;
n is an integer of 0 to 4;
m is an integer of 0 to 5;
when a plurality of R 1 and a plurality of R 2 are present, the plurality of R 1 and the plurality of R 2 each may be the same or different; and
Q represents any one selected from —O—, —S—, —CO—, —C(═O)O—, —SO 2 —, and —NHC(═O)—, wherein when Q is —C(═O)O— or —NHC(═O)—, Q may be in either direction.

5. The epoxy resin composition according to claim 1 , wherein the amount of the component [B] is 40 to 90% by mass, and the amount of the component [C] is 10 to 60% by mass, the percentages being based on the total amount of epoxy resin in the epoxy resin composition.

6. The epoxy resin composition according to claim 1 , further comprising diaminodiphenyl sulfone as a hardener.

7. The epoxy resin composition according to claim 1 , wherein a cured epoxy resin obtained by curing at 180° C. for 2 hours has a rubbery state elastic modulus of 15 MPa or less.

8. The epoxy resin composition according to claim 1 , wherein a cured epoxy resin obtained by curing at 180° C. for 2 hours has a flexural modulus of 4.5 GPa or more.

9. The epoxy resin composition according to claim 1 , wherein a cured epoxy resin obtained by curing at 180° C. for 2 hours has a rubbery state elastic modulus of 15 MPa or less and a flexural modulus of 4.5 GPa or more.

10. The epoxy resin composition according to claim 1 , further comprising a thermoplastic resin [D] soluble in the epoxy resin composition.

11. The epoxy resin composition according to claim 10 , comprising the component [D] in an amount of 1 to 40 parts by mass based on 100 parts by mass of the total amount of epoxy resin.

12. The epoxy resin composition according to claim 1 , further comprising a thermoplastic resin particle [E].

13. The epoxy resin composition according to claim 1 , having the curing calorific value of less than 400 J/g.

14. A prepreg obtained by impregnating carbon fibers with the epoxy resin composition according to claim 1 .

15. A carbon fiber-reinforced composite material obtained by curing the prepreg according to claim 14 .

16. A carbon fiber-reinforced composite material, comprising:
a cured epoxy resin obtained by curing the epoxy resin composition according to claim 1 ; and
a carbon fiber.

Assignees

• Toray Industries

Inventors

• Ueno Shizue
• Arai Nobuyuki
• Misumi Jun
• Taiko Hiroshi

Classifications

• C08K3/04

  Carbon · CPC title

• C08G59/4223

  aromatic · CPC title

• C08G59/3227

  Compounds containing acyclic nitrogen atoms · CPC title

• C08K7/06 Primary

  Elements · CPC title

• C08J2363/00

  Characterised by the use of epoxy resins; Derivatives of epoxy resins · CPC title