Production method for fibre-reinforced composite material, prepreg, particle-containing resin composition, and fibre-reinforced composite material

Patent metadata

Field	Value
Publication number	US-10316158-B2
Application number	US-201415037557-A
Country	US
Kind code	B2
Filing date	Oct 28, 2014
Priority date	Nov 19, 2013
Publication date	Jun 11, 2019
Grant date	Jun 11, 2019

Abstract

A production method for a fiber-reinforced composite material comprises: a step of stacking a prepreg plurally to obtain a prepreg-stacked body; and a step of heating the prepreg-stacked body to cure a resin, wherein the prepreg comprises: a reinforcing fiber layer including reinforcing fibers and a resin composition with which the space between fibers of the reinforcing fibers is impregnated and which contains (A) a benzoxazine resin, (B) an epoxy resin, and (C) a curing agent having 2 or more phenolic hydroxy groups in a molecule; and a surface layer provided on at least one surface of the reinforcing fiber layer and containing (A) to (C) components, and (D) polyamide resin particles having an average particle size of 5 to 50 μm.

First claim

The invention claimed is:

1. A production method for a fiber-reinforced composite material comprising:
stacking a prepreg plurally to obtain a prepreg-stacked body; and
heating the prepreg-stacked body to cure a resin,
wherein the prepreg comprises:
a reinforcing fiber layer including reinforcing fibers and a resin composition with which a space between fibers of the reinforcing fibers is impregnated and which contains (A) a benzoxazine resin, (B) an epoxy resin, and (C) a curing agent having 2 or more phenolic hydroxy groups in a molecule; and
a surface layer provided on at least one surface of the reinforcing fiber layer and containing (A) a benzoxazine resin, (B) an epoxy resin, (C) a curing agent having 2 or more phenolic hydroxy groups in a molecule, and (D) polyamide resin particles having an average particle size of 5 to 50 μm,
wherein the polyamide resin particles include (D1) first polyamide resin particles and (D2) second polyamide resin particles having a higher melting temperature measured in a composition constituting the surface layer than the melting temperature of the first polyamide resin particles
wherein a melting temperature of the (D1) first polyamide resin particles measured in the composition constituting the surface layer is 120 to 170° C.; and
a melting temperature of the (D2) second polyamide resin particles measured in the composition constituting the surface layer is 175 to 220° C.

2. The production method for a fiber-reinforced composite material according to claim 1 ,
wherein, when it is assumed that the melting temperature of the (D1) first polyamide resin particles measured in the composition constituting the surface layer is M 1 ° C. and
the melting temperature of the (D2) second polyamide resin particles measured in the composition constituting the surface layer is M 2 ° C.,
a value of (M 2 −M 1 ) is 5 or more.

3. The production method for a fiber-reinforced composite material according to claim 1 , wherein the surface layer contains 65 to 78 parts by mass of the (A) component, 22 to 35 parts by mass of the (B) component, 5 to 20 parts by mass of the (C) component, and 15 to 45 parts by mass of the (D) component when it is assumed that a total amount of the (A) component and the (B) component is 100 parts by mass.

4. The production method for a fiber-reinforced composite material according to claim 1 , wherein the (D1) first polyamide resin particles are polyamide 12 resin particles and the (D2) second polyamide resin particles are polyamide 1010 resin particles.

5. A prepreg comprising:
a reinforcing fiber layer including reinforcing fibers and a resin composition with which a space between fibers of the reinforcing fibers is impregnated and which contains (A) a benzoxazine resin, (B) an epoxy resin, and (C) a curing agent having 2 or more phenolic hydroxy groups in a molecule; and
a surface layer provided on at least one surface of the reinforcing fiber layer and containing (A) a benzoxazine resin, (B) an epoxy resin, (C) a curing agent having 2 or more phenolic hydroxy groups in a molecule, and (D) polyamide resin particles having an average particle size of 5 to 50 μm,
wherein the polyamide resin particles include (D1) first polyamide resin particles and (D2) second polyamide resin particles having a higher melting temperature measured in a composition constituting the surface layer than the melting temperature of the first polyamide resin particles,
wherein a melting temperature of the (D1) first polyamide resin particles measured in the composition constituting the surface layer is 120 to 170° C.; and
a melting temperature of the (D2) second polyamide resin particles measured in the composition constituting the surface layer is 175 to 220° C.

6. The prepreg according to claim 5 ,
wherein, when it is assumed that the melting temperature of the (D1) first polyamide resin particles measured in the composition constituting the surface layer is M 1 ° C. and
the melting temperature of the (D2) second polyamide resin particles measured in the composition constituting the surface layer is M 2 ° C.,
a value of (M 2 −M 1 ) is 5 or more.

7. The prepreg according to claim 5 , wherein the surface layer contains 65 to 78 parts by mass of the (A) component, 22 to 35 parts by mass of the (B) component, 5 to 20 parts by mass of the (C) component, and 15 to 45 parts by mass of the (D) component when it is assumed that a total amount of the (A) component and the (B) component is 100 parts by mass.

8. A fiber-reinforced composite material obtained by
stacking the prepreg according to claim 5 plurally, forming a plurality of sequential reinforcing layers and surface layers, and
performing heating under increased pressure.

9. The fiber-reinforced composite material according to claim 8 , wherein the (D1) first polyamide resin particles are polyamide 12 resin particles and the (D2) second polyamide resin particles are polyamide 1010 resin particles.

10. The fiber-reinforced composite material according to claim 8 , wherein the volume proportion {C 1 /(C 1 +C 2 )}×100 is 70% by volume or more, wherein:
(C 1 ) is the volume of polyamide resin contained between sequential reinforcing layers, and
(C2) is volume of polyamide resin contained in the reinforcing layers.

11. The fiber-reinforced composite material according to claim 8 , wherein the mode I interlaminar fracture toughness value (G1c) measured in accordance with ASTM D5528 is 300 J/m 2 or more.

12. The prepreg according to claim 5 , wherein the (D1) first polyamide resin particles are polyamide 12 resin particles and the (D2) second polyamide resin particles are polyamide 1010 resin particles.

13. A resin composition containing particles, comprising:
(A) a benzoxazine resin;
(B) an epoxy resin;
(C) a curing agent having 2 or more phenolic hydroxy groups in a molecule; and
(D) polyamide resin particles having an average particle size of 5 to 50 μm,
wherein the polyamide resin particles include polyamide 12 resin particles and polyamide 1010 resin particles.

14. The resin composition containing particles according to claim 13 , wherein the resin composition contains 65 to 78 parts by mass of the (A) component, 22 to 35 parts by mass of the (B) component, 5 to 20 parts by mass of the (C) component, and 15 to 45 parts by mass of the (D) component when it is assumed that a total amount of the (A) component and the (B) component is 100 parts by mass.

Assignees

• Jxtg Nippon Oil & Energy Corp
• Subaru Corp

Inventors

• Minami Masaki
• Matsumoto Takayuki
• Fukuda Yoshihiro
• Sekine Naoyuki
• Nakajima Masanori

Classifications

• B32B2260/046

  Synthetic resin · CPC title

• B29K2105/0872

  Prepregs · CPC title

• C08J2477/02

  Polyamides derived from omega-amino carboxylic acids or from lactams thereof (C08J2477/10 takes precedence) · CPC title

• C08J2477/06

  Polyamides derived from polyamines and polycarboxylic acids (C08J2477/10 takes precedence) · CPC title

• B32B2307/306

  Resistant to heat · CPC title