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

Patent metadata

Field	Value
Publication number	US-2016152785-A1
Application number	US-201414896865-A
Country	US
Kind code	A1
Filing date	Jul 10, 2014
Priority date	Jul 11, 2013
Publication date	Jun 2, 2016
Grant date	—

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

1 . An epoxy resin composition comprising [A1] and [B] below, 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:
[A1] a hardener represented by Formula (1)

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; and
[B] an aromatic epoxy resin having tri- or higher functionality.

2 . The epoxy resin composition according to claim 1 , wherein the component [A1] comprises particles having an average particle size of less than 20 μm.

3 . 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.

4 . The epoxy resin composition according to claim 1 , wherein X in Formula (1) of the component [A1] is —NHC(═O)—.

5 . 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):

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.

6 . The epoxy resin composition according to claim 1 , wherein n in Formula (2) or Formula (3) of the component [A1] is 1 to 3.

7 . An epoxy resin composition, comprising [A2] and [B]:
[A2] a hardener particle of an aromatic diamine compound having a structure represented by Formula (4), the particles having an average particle size of less than 20 μm:

wherein Y represents —NHC(═O)—, 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 Y may be in either direction; and
[B] an aromatic epoxy resin having tri- or higher functionality.

8 . The epoxy resin composition according to claim 7 , wherein the component [A2] is a hardener having a structure represented by Formula (5) or Formula (6):

wherein Y represents —NHC(═O)—, 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 Y may be in either direction.

9 . The epoxy resin composition according to claim 1 , having a curing calorific value, as determined by differential scanning calorimetry (DSC) at a temperature ramp rate of 5° C./min, of less than 450 J/g.

10 . An epoxy resin composition comprising [A3] and [B], wherein a carbon nuclear relaxation time T 1 C corresponding to a benzene ring carbon atom in the main backbone of Formula (7) assigned to 130 ppm in a solid-state 13 C-NMR spectrum is 40 seconds or longer:
[A3] a hardener represented by Formula (7)

wherein Z represents —C(═O)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 an a halogen atom, wherein Z may be in either direction; and
[B] an aromatic epoxy resin having tri- or higher functionality.

11 . The epoxy resin composition according to claim 10 , wherein n in Formula (7) of the component [A3] is 0.

12 . The epoxy resin composition according to claim 1 , wherein the component [B] is an epoxy resin represented by Formula (8):

wherein T represents any one selected from —CH 2 —, —O—, —CO—, —C(═O)O—, —S—, —SO 2 —, and —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 an a halogen atom, wherein when T is —C(═O)O— or —NHC(═O)—, T may be in either direction.

13 . The epoxy resin composition according to claim 12 , wherein T in Formula (8) of the component [B] is —SO 2 — or —NHC(═O)—.

14 . The epoxy resin composition according to claim 1 , wherein the amount of the component [B] is 40 to 90% by mass based on the total amount of epoxy resin in the epoxy resin composition.

15 . The epoxy resin composition according to claim 1 , wherein the equivalent ratio of all active hydrogens of amino groups in the component [A1], [A2], or [A3] to all epoxy groups in the epoxy resin composition is 0.5 to 0.9.

16 . The epoxy resin composition according to claim 1 , further comprising a component [C] below:
[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.

17 . The epoxy resin composition according to claim 16 , 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.

18 . The epoxy resin composition according to claim 16 , 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.

19 . The epo

Assignees

• Toray Industries

Inventors

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

Classifications

• C08G59/4223

  aromatic · CPC title

• B32B27/38

  comprising epoxy resins · CPC title

• C08J2363/02

  Polyglycidyl ethers of bis-phenols · CPC title

• C08G59/3227

  Compounds containing acyclic nitrogen atoms · CPC title

• C08J2363/00

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