IP Library Granted Patent US 9,856,354
Granted Patent B2
US 9,856,354 · App. 13/058,987 · Granted Jan 2, 2018

Epoxy resin composition and prepreg using the same, fiber-reinforced composite resin tubular body manufactured from the prepreg and manufacturing method therefor, and fiber-reinforced composite resin molded body

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Quick Facts
Patent No.
US 9,856,354
App. No.
13/058,987
Granted
Jan 2, 2018
Kind
B2
Abstract

By completing curing in a short period of time even at low temperatures and using an epoxy resin composition as a matrix resin of a prepreg, it is possible to obtain a fiber-reinforced composite plastic product such as a fiber-reinforced tubular composite with excellent mechanical properties and, more particularly, excellent impact resistance. The epoxy resin composition includes A component, B component, C component, D component and E component, where the content rate of sulfur atoms is equal to or more than 0.2 wt % and equal to or less than 7 wt %, and the content rate of the C component is equal to or more than 1 wt % and equal to or less than 15 wt %. A component: epoxy resins, B component: reactive products of the epoxy resins and an amine compounds including the sulfur atom in a molecule (the unreacted epoxy resins and/or the amine compounds may be included), C component: polyamide compounds soluble in the A component, D component: urea compounds, and E component: dicyandiamide.

Claims (50)

1. An epoxy resin composition, comprising:

an A component which is an epoxy resin;

a B component which is a reactive product of an epoxy resin, which is the same or different from the A component, and an amine compound comprising a sulfur atom;

a C component which is a block copolymer represented by formula (1) that is soluble in the A component;

a D component which is a urea compound; and

an E component which is a dicyandiamide,

wherein

a content of the sulfur atom is 0.2 wt % to 7 wt % relative to the epoxy resin composition,

a content of the C component is 1 wt % to 15 wt % relative to the epoxy resin composition, and

unreacted epoxy resin and/or unreacted amine compound may be present in the B component;

wherein

PE denotes a polyetherester skeleton,

PA denotes a polyamide skeleton and the polyamide skeleton is derived from a polymeric fatty acid,

X=1 to 10,

Y=1 to 10, and

Z=1 to 20.

2. A prepreg, comprising:

the epoxy resin composition according to claim 1 ,

wherein the prepreg is impregnated in a reinforcement fiber.

3. A fiber-reinforced composite plastic product, comprising:

the prepreg according to claim 2 .

4. A fiber-reinforced tubular composite, comprising:

the prepreg according to claim 2 .

5. The fiber-reinforced tubular composite according to claim 4 , wherein the fiber-reinforced tubular composite is a golf club shaft.

6. A method of manufacturing a fiber-reinforced tubular composite, the method comprising:

winding the prepreg according to claim 2 on a mandrel;

curing the epoxy resin composition in the prepreg;

and

separating the cured epoxy resin from the mandrel, thereby obtaining a fiber-reinforced tubular composite,

wherein

a temperature of the curing is 80 to 150° C., and

a length of the curing is 5 to 90 minutes.

7. The epoxy resin composition of claim 1 , wherein the A component is an epoxy resin selected from the group consisting of bisphenol A epoxy resin, a bisphenol F-epoxy resin, a biphenyl epoxy resin, a dicyclopentadiene-type epoxy resin, a difunctional epoxy resin, a phenol novolak epoxy resin, a cresol epoxy resin, a glycidylamine epoxy resin, a triglycidyl aminophenol, a tetraglycidylamine, a glycidylether epoxy resin, and a combination thereof.

8. The epoxy resin composition of claim 1 , wherein the A component is an epoxy resin selected from the group consisting of bisphenol A epoxy resin, the bisphenol F epoxy resin, a bisphenol S epoxy resin, a phenol novolak epoxy resin, a cresol novolak epoxy resin, and a combination thereof.

9. The epoxy resin composition of claim 1 , wherein the amine compound is selected from the group consisting of 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, bis(4-(4-aminophenoxy)phenyl) sulfone, bis(4-(3-aminophenoxy)phenyl) sulfone, 4′4-diaminodiphenyl sulfide, o-trian sulfone, and a combination thereof.

10. The epoxy resin composition of claim 1 , wherein the block copolymer represented by formula (1) is a polyetheresteramide wherein X=Y=1, Z=7.26.

11. The epoxy resin composition of claim 1 , wherein the urea compound is selected from the group consisting of dichlorodimethyl urea, a phenyldimethyl urea, and a combination thereof.

12. The epoxy resin composition of claim 1 , wherein the content of the C component is 2 to 10 wt %.

13. The epoxy resin composition of claim 1 , wherein the content of the C component is 2 to 6 wt %.

14. The epoxy resin composition of claim 1 , wherein the content of the A component is 10 to 90 wt % relative to the epoxy resin composition.

15. The epoxy resin composition of claim 1 , wherein the content of the A component is 30 to 90 wt % relative to the epoxy resin composition.

16. The epoxy resin composition of claim 1 , wherein the content of the D component is 1 to 15 wt % relative to the epoxy resin composition.

17. The epoxy resin composition of claim 1 , wherein the content of the E component is 0.1 to 10 wt % relative to the epoxy resin composition.

18. The epoxy resin composition of claim 1 , wherein the A component is an epoxy resin selected from the group consisting of bisphenol A epoxy resin, the bisphenol F epoxy resin, a bisphenol S epoxy resin, a phenol novolak epoxy resin, a cresol novolak epoxy resin, and a combination thereof,

wherein the amine compound is selected from the group consisting of 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, bis(4-(4-aminophenoxy)phenyl) sulfone, bis(4-(3-aminophenoxy)phenyl) sulfone, 4′4-diaminodiphenyl sulfide, o-trian sulfone, and a combination thereof,

wherein the block copolymer represented by formula (1) is a polyetheresteramide wherein X=Y=1, Z=7.26,

wherein the urea compound is selected from the group consisting of dichlorodimethyl urea, a phenyldimethyl urea, and a combination thereof,

wherein the content of the C component is 2 to 6 wt %,

wherein the content of the D component is 1 to 15 wt % relative to the epoxy resin composition, and

wherein the content of the E component is 0.1 to 10 wt % relative to the epoxy resin composition.

Assignments (2)
CORPORATE NAME CHANGE Recorded Jun 19, 2017
From: MITSUBISHI RAYON CO., LTD.
To: MITSUBISHI CHEMICAL CORPORATION
Reel/Frame 042886/0294 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 22, 2011
From: MIWA, YOUHEI; SAITOU, TADAYOSHI; TAGUCHI, MASATO; UCHIZONO, MIKIHIRO; ATSUMI, TETSUYA; IBUKI, TSUTOMU
To: MITSUBISHI RAYON CO., LTD.; MRC COMPOSITE PRODUCTS CO., LTD.
Reel/Frame 025843/0291 →