Carbon fiber forming raw material, formed material, and carbon fiber-reinforced composite material

Patent metadata

Field	Value
Publication number	US-10184034-B2
Application number	US-201214362533-A
Country	US
Kind code	B2
Filing date	Nov 12, 2012
Priority date	Dec 5, 2011
Publication date	Jan 22, 2019
Grant date	Jan 22, 2019

Abstract

The carbon fiber forming raw material is a carbon fiber forming raw material (Z) as a prepreg including sizing agent-coated carbon fibers and a thermosetting resin or a carbon fiber forming raw material (Y) as a forming material that includes sizing agent-coated carbon fibers and has a woven fabric form or a braid form. The sizing agent includes components (A) and (B). The component (A) is an epoxy compound having two or more epoxy groups or two or more types of functional groups. The component (B) is one or more compounds selected from the group consisting of a tertiary amine compound, a tertiary amine salt, a quaternary ammonium salt, a quaternary phosphonium salt, and a phosphine compound. The component (B) is contained in an amount of 0.1 to 25 parts by mass relative to 100 parts by mass of the component (A).

First claim

The invention claimed is:

1. A carbon fiber forming raw material including sizing agent-coated carbon fiber bundles coated with a sizing agent, the carbon fiber forming raw material having a woven fabric form or a braid form,
the carbon fiber forming raw material comprising:
carbon fiber bundles made of carbon fiber; and
the sizing agent which is coated on the carbon fiber bundles so that a film of the sizing agent is formed on the carbon fiber bundles;

wherein the carbon fibers have a surface oxygen concentration O/C of 0.05 to 0.5 determined by X-ray photoelectron spectroscopy;
wherein the thickness of the sizing agent applied to the carbon fiber and dried is in a range of 2 to 20 nm;
wherein the sizing agent comprises:
a component (A) including
an epoxy compound (A1) having an epoxy equivalent of less than 360 g/mol and having two or more epoxy groups which is a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol A epoxy resin, or a tetraglycidyldiaminodiphenylmethane and/or
an epoxy compound (A2) which is at least one selected from the group consisting of sorbitol polyglycidyl ethers, glycerol polyglycidyl ethers, glycidylbenzamide, amide-modified epoxy resins, glycidylphthalimide, urethane-modified epoxy resins, bisphenol S epoxy resins, glycidyl p-toluenesulfonate, and glycidyl 3-nitrobenzenesulfonate; and

a reaction accelerator component (B1) being contained in an amount of 1 to 20 parts by mass relative to 100 parts by mass of the component (A), said reaction accelerator component (B1) selected from the group consisting of: N,N-dimethylbenzylamine; 1,8-bis(dimethylbenzylamine); 1,8-bis(dimethylamino)naphthalene; 1,5 diazabicyclo [4, 3, 0]-5-nonene, 1-benzyl-imidazole; 1,8-diazabicyclo[5,4,0]-7-undecene phenol salt; 1,8-diazabicyclo[5,4,0]-7-undecene octanoate; 1,8-diazabicyclo[5,4,0]-7-undecene p-toluenesulfonate; N-ethylmorpholine; 2,6-lutidine; 4-pyridinemethanol; triisopropanolamine; and triethanolamine; and
wherein the amount of sizing agent coated on the carbon fibers is in a range of from 0.1 to 10 parts by mass of sizing agent relative to 100 parts by mass of carbon fibers.

2. The carbon fiber forming raw material according to claim 1 , wherein the component (A) is an epoxy compound having three or more epoxy groups.

3. The carbon fiber forming raw material according to claim 1 , wherein the carbon fibers are obtained by liquid phase electrolytic oxidation in an alkaline electrolytic solution or liquid phase electrolytic oxidation in an acid electrolytic solution and then washing the resulting fibers with an alkaline aqueous solution.

4. A formed material obtained by combining the forming base material according to claim 1 with a thermosetting resin or a thermoplastic resin.

5. A carbon fiber-reinforced composite material obtained by forming the carbon fiber forming raw material according to claim 1 .

6. A carbon fiber-reinforced composite material obtained by forming the formed material as claimed in claim 4 .

7. A sizing agent coated carbon fiber material formed by subjecting the carbon fiber forming raw material according to claim 1 to a thermal treatment at 160 to 260° C. for 30 to 600 seconds.

8. A prepreg including sizing agent-coated carbon fiber bundles coated with a sizing agent and a thermosetting matrix resin,
A) the carbon fiber forming raw material comprising:
carbon fiber bundles made of carbon fiber; and
the sizing agent which is coated on the carbon fiber bundles so that a film of the
sizing agent is formed on the carbon fiber bundles;

wherein the carbon fibers have a surface oxygen concentration O/C of 0.05 to 0.5 determined by X-ray photoelectron spectroscopy;
wherein the thickness of the sizing agent applied to the carbon fiber and dried is in a range of 2 to 20 nm;
wherein the sizing agent comprises:
a component (A) including
an epoxy compound (A1) having an epoxy equivalent of less than 360 g/mol and having two or more epoxy groups which is a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol A epoxy resin, or a tetraglycidyldiaminodiphenylmethane and/or
an epoxy compound (A2) which is at least one selected from the group consisting of sorbitol polyglycidyl ethers, glycerol polyglycidyl ethers, glycidylbenzamide, amide-modified epoxy resins, glycidylphthalimide, urethane-modified epoxy resins, bisphenol S epoxy resins, glycidyl p-toluenesulfonate, and glycidyl 3-nitrobenzenesulfonate; and

a reaction accelerator component (B1) being contained in an amount of 1 to 20 parts by mass relative to 100 parts by mass of the component (A), said reaction accelerator component (B1) selected from the group consisting of: N,N-dimethylbenzylamine; 1,8-bis(dimethylbenzylamine); 1,8-bis(dimethylamino)naphthalene; 1,5 diazabicyclo [4, 3, 0]-5-nonene, 1-benzyl-imidazole; 1,8-diazabicyclo[5,4,0]-7-undecene phenol salt; 1,8-diazabicyclo[5,4,0]-7-undecene octanoate; 1,8-diazabicyclo[5,4,0]-7-undecene p-toluenesulfonate; N-ethylmorpholine; 2,6-lutidine; 4-pyridinemethanol; triisopropanolamine; and triethanolamine; and
wherein the amount of sizing agent coated on the carbon fibers is in a range of from 0.1 to 10 parts by mass of sizing agent relative to 100 parts by mass of carbon fibers,
B) the thermosetting matrix resin comprising polyester resin, vinyl ester resin, epoxy resin, or polyimide, polyester or acid modified polyolefin.

9. The prepreg according to claim 8 , wherein the thermosetting resin is an epoxy resin.

10. The prepreg according to claim 8 , wherein the thermosetting resin contains a multifunctional glycidylamine epoxy resin and an aromatic diamine curing agent.

11. The prepreg according to claim 8 , wherein the thermosetting resin contains a dicyclopentadiene epoxy resin (D), an epoxy resin (E) having an average epoxy equivalent of 1,000 or more and 10,000 or less, and a curing agent (F).

12. The prepreg according to claim 8 , wherein the thermosetting resin contains 10 to 60 parts by mass of an amine epoxy resin, 40 to 90 parts by mass of a bisphenol epoxy resin, 1 to 10 parts by mass of dicyandiamide or a derivative thereof, and 1 to 10 parts by mass of at least one block copolymer (G) selected from the group consisting of S—B-M, B-M, and M-B-M.

13. The prepreg according to claim 8 , wherein the thermosetting resin is an epoxy matrix resin containing a bisphenol epoxy resin (H) having a softening point of 90° C. or more, an amine epoxy resin (I) having three or more functional groups, a bisphenol F epoxy resin (J) having a number average molecular weight of 450 or less, and a curing agent (K) and contains 20 to 50 parts by mass of the component (H), 30 to 50 parts by mass of the component (I), and 10 to 40 parts by mass of the component (J) relative to 100 parts by mass of the total amount of the components (H) to (J).

14. The prepreg according to claim 8 , wherein the prepreg satisfies at least one requirement of:
(1) thermoplastic resin particles or fibers (L) and electrically conductive particles or fibers (M) are further contained, and the mass ratio represented by [amount (parts by mass) of (L)]/[amount (parts by mass) of (M)] is 1 to 1,000; and
(2) electrically conductive particles or fibers (N) in which a thermoplastic resin nucleus or core is coated with an electrically conductive substance are further contained.

15. The prepreg according to claim 8 , wherein the prepreg has a width of 1 to 50 mm.

Assignees

• Toray Industries

Inventors

• Nakayama Yoshifumi
• Kamae Toshiya
• Kobayashi Daigo
• Endo Makoto

Classifications

• Y10T442/2008

  Fabric composed of a fiber or strand which is of specific structural definition · CPC title

• Y10T428/2918

  including free carbon or carbide or therewith [not as steel] · CPC title

• C08J2363/04

  Epoxynovolacs · CPC title

• C08J2363/02

  Polyglycidyl ethers of bis-phenols · CPC title

• C08J5/06 Primary

  using pretreated fibrous materials · CPC title