Prepreg and carbon fiber-reinforced composite material

Patent metadata

Field	Value
Publication number	US-11111345-B2
Application number	US-201715669794-A
Country	US
Kind code	B2
Filing date	Aug 4, 2017
Priority date	Jul 25, 2012
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

A prepreg includes; sizing agent-coated carbon fibers coated with a sizing agent; and a thermosetting resin composition impregnated into the sizing agent-coated carbon fibers. The sizing agent includes an aliphatic epoxy compound (A) and an aromatic compound (B) at least containing an aromatic epoxy compound (B1). The thermosetting resin composition includes a thermosetting resin (D) and a latent hardener (E), and optionally includes an additive (F) other than the thermosetting resin (D) and the latent hardener (E). The (a)/(b) ratio is within a predetermined range where (a) is the height of a component at a binding energy assigned to CHx, C—C, and C═C and (b) is the height of a component at a binding energy assigned to C—O in a C1s core spectrum of the surfaces of the sizing agent-coated carbon fibers analyzed by X-ray photoelectron spectroscopy.

First claim

The invention claimed is:

1. A prepreg comprising:
sizing agent-coated carbon fiber bundles coated with a sizing agent; and
a thermosetting resin composition impregnated into the sizing agent-coated carbon fiber bundles,

wherein
the sizing agent includes an aliphatic epoxy compound (A) and an aromatic compound (B) at least containing an aromatic epoxy compound (B1),
the aliphatic epoxy compound (A) and the aromatic epoxy compound (B1) are contained in a mass ratio of 52/48 to 80/20,
the aliphatic epoxy compound (A) comprises a glycidyl ether epoxy compound obtained by reaction of epichlorohydrin with a polyol selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, polybutylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, glycerol, diglycerol, polyglycerol, trimethylolpropane, pentaerythritol, sorbitol, and arabitol,
the sizing agent has an epoxy equivalent of 350 to 550 g/eq,
the sizing agent-coated carbon fiber bundles have an (a)/(b) ratio of 0.50 to 0.90, where (a) is a height (cps) of a component at a binding energy (284.6 eV) assigned to CHx, C—C, and C═C and (b) is a height (cps) of a component at a binding energy (286.1 eV) assigned to C—O in a C 1s core spectrum of a surface of the sizing agent applied onto the carbon fiber bundles analyzed by X-ray photoelectron spectroscopy using AlKα 1,2 as an X-ray source at a photoelectron takeoff angle of 15°,
the thermosetting resin composition is an epoxy resin composition at least containing
an epoxy resin (D11) of Formula (3) below and
an epoxy resin (D12) of Formula (4) below, and
the epoxy resin composition contains the epoxy resin (D11) in an amount of 25 to 50% by mass and the epoxy resin (D12) in an amount of 40 to 80% by mass relative to 100% by mass of the total epoxy resins contained,

the thermosetting resin composition includes a latent hardener which is an aromatic amine hardener (E2) that is used in combination with the sizing agent, and if the sizing agent and the aromatic amine hardener (E2) are mixed in an amine equivalent/epoxy equivalent ratio of 0.9 to form a first mixture, and the first mixture is stored in an atmosphere of 25° C. and 60% RH for 20 days, then the glass transition point of the first mixture will increase by 25° C. or less,
wherein the epoxy resin (D11) has a structure of Formula (3):

wherein in Formula (3),
each of R 8 and R 9 is at least one selected from the group consisting of C 1-4 aliphatic hydrocarbon groups, C 3-6 alicyclic hydrocarbon groups, C 6-10 aromatic hydrocarbon groups, halogen atoms, acyl groups, 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 8 s or R 9 s exist, R 8 s and R 9 s are each optionally the same or different; and
Z is one selected from —O—, —S—, —CO—, —C(═O)O—, —SO 2 —, and —C(═O)NH—); and

wherein the epoxy resin (D12) has a structure of Formula (4):

wherein in Formula (4),
R 10 to R 13 are at least one selected from the group consisting of a hydrogen atom, C 1-4 aliphatic hydrocarbon groups, alicyclic hydrocarbon groups having a carbon number of 4 or less, and halogen atoms; and
Y is one selected from —CH 2 —, —O—, —S—, —CO—, —C(═O)O—, —SO 2 —, and —C(═O)NH—.

2. The prepreg according to claim 1 , wherein the thermosetting resin composition is an epoxy resin composition at least containing an epoxy resin (D1) as the thermosetting resin (D) and a compound (E1) of General Formula (2):

(in Formula (2), R 4 to R 7 are at least one selected from the group consisting of a hydrogen atom, C 1-4 aliphatic hydrocarbon groups, alicyclic hydrocarbon groups having a carbon number of 4 or less, and halogen atoms; and X is one selected from —O—, —S—, —CO—, —C(═O)O—, and —C(═O)NH—) as the latent hardener (E).

3. The prepreg according to claim 1 , wherein
the thermosetting resin composition is an epoxy resin composition at least containing an epoxy resin (D1) as the thermosetting resin (D) and at least one block copolymer (F2) selected from the group consisting of S-B-M, B-M, and M-B-M as the additive (F),
the blocks in the block copolymer (F2) are linked through a covalent bond or linked through covalent bonds with an intermediate molecule having any chemical structure interposed therebetween,
the block M is a homopolymer of methyl methacrylate or a copolymer containing methyl methacrylate in an amount of at least 50% by mass,
the block B is incompatible with the block M and has a glass transition temperature of 20° C. or lower, and
the block S is incompatible with the blocks B and M and has a glass transition temperature higher than that of the block B.

4. The prepreg according to claim 1 , wherein
the thermosetting resin composition is an epoxy resin composition at least containing an epoxy resin (D132) having a softening point of 90° C. or higher, an epoxy resin (D152) having a softening point of 50° C. or lower, an epoxy resin (D142) having a softening point of 50° C. or lower and having a solubility parameter (SP) value that is 1.2 or more larger than an SP value of the epoxy resin (D132) and an SP value of the epoxy resin (D152) as the thermosetting resin (D),
an epoxy resin hardened product obtained by hardening the epoxy resin composition has a phase separated structure including a phase rich in the epoxy resin (D132) and a phase rich in the epoxy resin (D142), and
the phase separated structure has a phase separated structure period of 1 nm to 5 mm.

5. The prepreg according to claim 1 , wherein the sizing agent contains at least the aliphatic epoxy compound (A) in an amount of 35 to 65% by mass and the aromatic compound (B) in an amount of 35 to 60% by mass relative to a total amount of the sizing agent except solvents.

6. The prepreg according to claim 1 , wherein the aromatic epoxy compound (B1) is a bisphenol A epoxy compound or a bisphenol F epoxy compound.

7. The prepreg according to claim 1 , wherein the sizing agent contains an ester compound (C) having no epoxy group in a molecule in an amount of 2 to 35% by mass relative to a total amount of the sizing agent except solvents.

8. The prepreg according to claim 1 , wherein the sizing agent-coated carbon fibers satisfy relation (III):
0.50≤( I )≤0.90 and 0.60<( II )/( I )<1.0  (III)

wherein
(I) is a value of (a)/(b) of surfaces of the sizing agent-coated carbon fibers before ultrasonication, and
(II) is a value of (a)/(b) of the surfaces of the sizing agent-coated carbon fibers where an adhesion amount of the sizing agent is reduced to 0.09 to 0.20% by mass by ultrasonic cleaning of the sizing agent-coated carbon fibers in an acetone solvent, (a) is the height (cps) of a component at a binding energy (284.6 eV) assigned to CHx, C—C, and C═C, and (b) is the height (cps) of a component at a binding energy (286.1 eV) assigned to C—O in a C 1s core spectrum of the sizing agent-coated carbon fibers analyzed by X-ray photoelectron spectroscopy using an X-ray at 400 eV at a photoelectron takeoff angle of 55°.

9. The prepreg according to claim 1 , wherein Z is —O— in Formula (3).

10. The prepreg accor

Assignees

• Toray Industries

Inventors

• Arai Nobuyuki
• Ichikawa Tomoko
• Taiko Hiroshi
• Endo Makoto
• Kobayashi Masanobu
• Misumi Jun

Classifications

• C08G59/38 Primary

  together with di-epoxy compounds · CPC title

• C08J5/248

  using pre-treated fibres · CPC title

• D06M2101/40

  Fibres of carbon · CPC title

• D06M13/11

  Compounds containing epoxy groups or precursors thereof · CPC title

• C08K5/1515

  Three-membered rings · CPC title