Epoxy resin composition, prepreg, and roll made of resin reinforced with reinforcing fibers

• US 6,620,510 B1
• Filed: 06/25/2001
• Issued: 09/16/2003
• Est. Priority Date: 12/25/1998
• Status: Expired due to Term

• Current Assignee: Mitsubishi Chemical Corporation (Mitsubishi Chemical Group Corp.)
• Original Assignee: Mitsubishi Rayon Company Limited (Mitsubishi Chemical Holdings Corporation)
• Inventors: Yamaguchi, Yutaka, Koba, Hisao, Taguchi, Masato
• Primary Examiner(s): Dawson, Robert
• Assistant Examiner(s): Feely, Michael J
• Application Number:
  US09/869,127
• Time in Patent Office: 813 Days
• Field of Search: 523/400, 523/427, 523/428, 525/107, 428/34.1, 428/34.6, 428/34.7, 428/35.7, 428/35.9, 428/297.4, 428/300.7, 428/320.2, 428/413, 428/414
• US Class Current: 428/413
• CPC Class Codes: C08J 2363/00 Characterised by the use of epoxy resins; Derivatives of epoxy resins
• CPC Class Codes: C08J 5/243 using carbon fibres
• CPC Class Codes: C08J 5/249 characterised by the additives used in the prepolymer mixture
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: F16C 13/00 Rolls, drums, discs, or the like guide rollers in feeding webs B65H27/00; calender rolls, bearings therefor D21G1/02; rotary drums or rollers for heat-exchange or heat-transfer apparatus F28F5/02; Bearings or mountings therefor
• CPC Class Codes: F16C 3/026 Shafts made of fibre reinforced resin
• CPC Class Codes: Y10T 428/13 Hollow or container type article [e.g., tube, vase, etc.]
• CPC Class Codes: Y10T 428/1317 Multilayer [continuous layer]
• CPC Class Codes: Y10T 428/1321 Polymer or resin containing [i.e., natural or synthetic]
• CPC Class Codes: Y10T 428/1352 Polymer or resin containing [i.e., natural or synthetic]
• CPC Class Codes: Y10T 428/1359 Three or more layers [continuous layer]
• CPC Class Codes: Y10T 428/24994 Fiber embedded in or on the surface of a polymeric matrix
• CPC Class Codes: Y10T 428/24995 Two or more layers
• CPC Class Codes: Y10T 428/249994 Composite having a component wherein a constituent is liquid or is contained within preformed walls [e.g., impregnant-filled, previously void containing component, etc.]
• CPC Class Codes: Y10T 428/31511 Of epoxy ether

Abstract

An epoxy resin composition giving a cured resin plate which, after 60 hour standing at 150° C. and at the saturated vapor pressure, has a water absorption of 3.5% by weight or lower; a prepreg which comprises the epoxy resin composition and reinforcing fibers; and a fiber-reinforced resin roll which is 1) a laminate comprising fiber-reinforced resin layers each comprising reinforcing fibers and a matrix resin, wherein the matrix resin is a resin composition giving a cured resin plate which, after 60 hour standing at 150° C. and at the saturated vapor pressure, has a water absorption of 3.5% by weight or lower; or 2) a laminate comprising (i) at least one fiber-reinforced resin layer comprising long reinforcing fibers having an elastic modulus of 600˜800 Gpa and a resin composition and (ii) at least one fiber-reinforced resin layer comprising long reinforcing fibers having an elastic modulus of 140˜300 Gpa and a resin composition.

Claims

1. An epoxy resin composition having a water absorption rate of no greater than 3.5% by weight,

wherein the water absorption rate is the water absorption rate of a resin board cured at 180°

C. for three hours to form a cured resin board of 2 mm thickness then cut into a 60 mm×

12 mm×

2 mm test piece and exposed to a saturated vapor at 150°

C. for 60 hours.

2. The epoxy resin composition according to claim 1, further satisfying the following condition (b):

(b) the test piece has a rigidity as measured by a ratio (LogG′

after)/(LogG′

before) of not less than 0.95, wherein (LogG′

after) is the rigidity of the test piece at 150°

C. after sitting for 60 hours under a saturated vapor at 150°

C. and (LogG′

before) is the rigidity of the test piece at 150°

C. prior to sitting for 60 hours under a saturated vapor at 150°

C.

3. The epoxy resin composition according to claim 1, further satisfying the following condition (c):

(c) a glass transition temperature of the test piece is 150-200°

C.

4. A prepreg, comprising:

an epoxy resin composition according to claim 1; and

reinforcing fibers.

5. A An epoxy resin composition, comprising:

a resin component (X) comprising

20 to 59% by weight of a bisphenol epoxy resin (A) which is in an aqueous state at room temperature;

25 to 50% by weight of an epoxy resin (B) comprising at least one repeating unit selected from the group consisting of the following formulae 1-4

15 to 40% by weight of an epoxy resin (C) modified by crosslinked rubber granules having an average diameter of no greater than 1 μ

m; and

1 to 10% by weight of a thermoplastic resin (D) that is soluble in a mixture of said epoxy resin (A) and said epoxy resin (B); and

a diamino diphenylsulfone (E) in the amount of 20 to 50 parts by weight based on 100 parts by weight of said resin component (X);

wherein a viscosity of said epoxy resin composition at 60°

C. is 500 to 3000 poise.

6. The epoxy resin composition according to claim 5, further comprising:

5 to 50 parts by weight of an epoxy resin (F) which is different from said epoxy resin (B) and has a softening point of at least 70°

C., wherein parts by weight is based on 100 parts by weight of said resin component (X).

7. A cylindrical or tubular roll of a resin reinforced with reinforcing fibers, formed by laminating a plurality of layers of resins reinforced with reinforcing fibers, said cylindrical or tubular roll of a resin comprising:

reinforcing fibers; and

a matrix resin;

wherein said matrix resin comprises an epoxy resin composition having a water absorption rate of no greater than 3.5% by weight,

wherein the water absorption rate is the water absorption rate of a resin board cured at 180°

C. for three hours to form a cured resin board of 2 mm thickness then cut into a 60 mm×

12 mm×

2 mm test piece and exposed to a saturated vapor at 150°

C. for 60 hours.

8. The cylindrical or tubular roll of a resin reinforced with reinforcing fibers according to claim 7, wherein said epoxy resin composition satisfies the following condition (b):

(b) a cured board of 60 mm×

12 mm×

2 mm has a ratio (LogG′

after)/(LogG′

before) of not less than 0.95, wherein (LogG′

after) at 150°

C. is the rigidity of said cured resin board after sitting for 60 hours under a saturated vapor at 150°

C. and (LogG′

before) is the rigidity at 150°

C. of said cured resin board before sitting for 60 hours under a saturated vapor at 150°

C.

9. The cylindrical or tubular roll of a resin reinforced with reinforcing fibers according to claim 7, wherein said epoxy resin composition satisfies the following condition (c):

(c) a glass transition temperature of the test piece is 150-200°

C.

10. A cylindrical or tubular roll of a resin reinforced with reinforcing fibers, formed by laminating a plurality of layers of resins reinforced with reinforcing fibers, said cylindrical or tubular roll of a resin comprising:

reinforcing fibers; and

a matrix resin;

wherein said matrix resin comprises an epoxy resin composition comprising

a resin component (X) comprising

20 to 59% by weight of a bisphenol epoxy resin (A) which is in an aqueous state at room temperature;

25 to 50% by weight of an epoxy resin (B) comprising at least one repeating unit selected from the group consisting of the following formulae 1-4

15 to 40% by weight of an epoxy resin (C) modified by crosslinked rubber granules having an average diameter of no greater than 1 μ

m; and

1 to 10% by weight of a thermoplastic resin (D) that is soluble in a mixture of said epoxy resin (A) and said epoxy resin (B); and

a diamino diphenylsulfone (E) in the amount of 20 to 50 parts by weight based on 100 parts by weight of said resin component (X);

wherein a viscosity of said epoxy resin composition at 60°

C. is 500 to 3000 poise.

11. The cylindrical or tubular roll of a resin reinforced with reinforcing fibers according to claim 10, wherein said epoxy resin composition further comprises

5 to 50 parts by weight of an epoxy resin (F) which is different from said epoxy resin (B) and has a softening point of least 70° C., wherein parts by weight is based on 100 parts by weight of said resin component (X).

12. A cylindrical or tubular roll of a resin reinforced with reinforcing fibers, comprising:

at least one layer (I) of a resin reinforced with reinforcing fibers comprising long reinforcing fibers having an elastic modulus of 600 to 800 GPa, and an epoxy resin composition;

at least one layer (II) of a resin reinforced with reinforcing fibers comprising long reinforcing fibers having an elastic modulus of 140 to 300 GPa, and an epoxy resin composition for supporting said roll of a resin reinforced with reinforcing fibers in a circumferential direction;

wherein a weight ratio of said long reinforcing fibers having an elastic modulus of 600 to 800 GPa to said long reinforcing fibers having an elastic modulus of 140 to 300 GPa is 2/3 to 4/1.

13. The cylindrical or tubular roll of a resin reinforced with reinforcing fibers according to claim 12, wherein said epoxy resin composition has a water absorption rate of no greater than 3.5% by weight,

wherein the water absorption rate is the water absorption rate of a resin board cured at 180° C. for three hours to form a cured resin board of 2 mm thickness then cut into a 60 mm×

12 mm×

2 mm test piece and exposed to a saturated vapor at 150°

C. for 60 hours.

14. The cylindrical or tubular roll of a resin reinforced with reinforcing fibers according to claim 12, wherein said epoxy resin composition satisfies the following condition (b):

(b) a cured board of 60 mm×

12 mm×

2 mm has a ratio (LogG′

after)/(LogG′

before) of not less than 0.95, wherein (LogG′

after) is the rigidity at 150°

C. of said cured resin board after sitting for 60 hours under a saturated vapor at 150°

C. and (LogG′

before) is the rigidity at 150°

C. of said cured resin board before sitting for 60 hours under a saturated vapor at 150°

C.

15. The cylindrical or tubular roll of a resin reinforced with reinforcing fibers according to claim 12, wherein said epoxy resin composition satisfies the following condition (c):

(c) a glass transition temperature of the cured resin board obtained by means of curing said resin composition is 150˜

200°

C.

16. The cylindrical or tubular roll of a resin reinforced with reinforcing fibers according to claim 12, wherein said epoxy resin composition comprises:

a resin component (X) comprising

20 to 59% by weight of a bisphenol epoxy resin (A) which is in an aqueous state at room temperature;

25 to 50% by weight of an epoxy resin (B) comprising at least one repeating unit selected from the group consisting of the following formulae 1-4

15 to 40% by weight of an epoxy resin (C) modified by crosslinked rubber granules having an average diameter of no greater than 1 μ

m; and

1 to 10% by weight of a thermoplastic resin (D) that is soluble in a mixture of said epoxy resin (A) and said epoxy resin (B); and

a diamino diphenylsulfone (E) in the amount of 20 to 50 parts by weight based on 100 parts by weight of said resin component (X);

wherein a viscosity of said epoxy resin composition at 60°

C. is 500 to 3000 poise.

17. The cylindrical or tubular roll of a resin reinforced with reinforcing fibers according to claim 16, wherein said epoxy resin composition further comprises

5 to 50 parts by weight of an epoxy resin (F) which is different from said epoxy resin (B) and has a softening point of least 70°

C., wherein parts by weight is based on 100 parts by weight of said resin component (X).