Molding material and production process

• US 20020019182A1
• Filed: 09/18/2001
• Published: 02/14/2002
• Est. Priority Date: 11/06/1996
• Status: Active Grant

• Current Assignee: Toray Industries Incorporated
• Original Assignee: Toray Industries Incorporated
• Inventors: Ishibashi, Soichi, Kyono, Tetsuyuki
• Granted Patent: US 6,828,374 B2
• Time in Patent Office: Days
• US Class Current: 442/59
• CPC Class Codes: B29B 15/122 with a matrix in liquid form, e.g. as melt, solution or latex
• CPC Class Codes: B29B 7/88 Adding charges , i.e. additives
• CPC Class Codes: B29B 7/90 Fillers or reinforcements , e.g. fibres
• CPC Class Codes: B29B 9/14 fibre-reinforced
• CPC Class Codes: B29C 45/00 Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor injection blow-moulding B29C49/06
• CPC Class Codes: B29C 70/50 for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
• CPC Class Codes: C08K 7/02 Fibres or whiskers
• CPC Class Codes: C08K 7/14 Glass
• CPC Class Codes: C08L 23/02 not modified by chemical after-treatment
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 77/00 Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain of polyhydrazides C08L79/06; of polyamideimides or polyamide acids C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: Y10T 428/249928 Fiber embedded in a ceramic, glass, or carbon matrix
• CPC Class Codes: Y10T 428/24993 Fiber is precoated
• CPC Class Codes: Y10T 428/249937 Fiber is precoated
• CPC Class Codes: Y10T 428/249938 Composite or conjugate fiber [e.g., fiber contains more than one chemically different material in monofilament or multifilament form, etc.]
• CPC Class Codes: Y10T 428/249939 Two or more layers
• CPC Class Codes: Y10T 428/24994 Fiber embedded in or on the surface of a polymeric matrix
• CPC Class Codes: Y10T 428/249948 Fiber is precoated
• CPC Class Codes: Y10T 428/24995 Two or more layers
• CPC Class Codes: Y10T 428/249952 At least one thermosetting synthetic polymeric material layer
• CPC Class Codes: Y10T 428/292 : In coating or impregnation
• CPC Class Codes: Y10T 428/2924 : Composite
• CPC Class Codes: Y10T 428/2929 : Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
• CPC Class Codes: Y10T 428/2933 : Coated or with bond, impregnation or core
• CPC Class Codes: Y10T 428/2935 : Discontinuous or tubular or cellular core
• CPC Class Codes: Y10T 428/2936 : Wound or wrapped core or coating [i.e., spiral or helical]
• CPC Class Codes: Y10T 428/2973 : Particular cross section
• CPC Class Codes: Y10T 442/20 : Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
• CPC Class Codes: Y10T 442/2369 : Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric

Abstract

The present invention provides a molding material which is easy to produce and allows a reinforcing fiber bundle to be well dispersed in the molded product obtained by injection molding, etc., a production process thereof, a polyamide based resin composition with good flowability, and molded products obtained from them.

A molding material, comprising at least the following components [A], [B] and [C], with the component [C] arranged to contact a composite comprising the components [A] and [B].

[A] A continuous reinforcing fiber bundle

[B] A thermoplastic polymer or oligomer with a weight average molecular weight of 200 to 50,000 and a melt viscosity lower than that of the component [C]

[C] A thermoplastic resin with a weight average molecular weight of 10,000 or more.

Claims

1. A molding material, comprising at least the following components [A], [B] and [C], with the component [C] arranged to contact a composite comprising the components [A] and [B].

[A] A continuous reinforcing fiber bundle

[B] A thermoplastic polymer or oligomer with a weight average molecular weight of 200 to 50,000 and a melt viscosity lower than that of the component [C]

[C] A thermoplastic resin with a weight average molecular weight of 10,000 or more.

2. A molding material, according to claim 1, wherein the molding material is cut at a length of 1 to 50 mm.

3. A molding material, according to claim 1, wherein the component [C] is arranged to cover the surrounding of the composite.

4. A molding material, according to claim 3, wherein the molding material is cut at a length of 1 to 50 mm.

5. A molding material, according to claim 1, wherein the component [C] is arranged with the composite in layers.

6. A molding material, according to claim 5, wherein the molding material is cut at a length of 1 to 50 mm.

7. A molding material, according to any one of claims 1 through b, wherein the melt viscosity of the component [B] is 100 poises or less, and the melt viscosity of the component [C] is 500 poises or more.

8. A molding material, according to any one of claims 1 through 6, wherein the absolute value of the difference between the solubility parameter δ

1 of the component [B] and the solubility parameter δ

2 of the component [C] is smaller than 3.5.

9. A molding material, according to any one of claims 1 through 6, wherein when the content of the component [B] in the molding material is 10 wt %, the Izod impact value of the molded product obtained by molding the molding material accounts for 60% or more of the Izod impact value of the molded product obtained by excluding the component [B] from the components of the molding material.

10. A molding material, according to any one of claims 1 through 6, wherein the volumetric content of the component [A] in the composite is 40 to 95%.

11. A molding material, according to any one of claims 1 through 6, wherein the void volume of the composite is 0 to 40%.

12. A molding material, according to any one of claims 1 through 6, wherein the component [C] is a polyamide, polyolefin, polycarbonate, or any of the mixtures and copolymers comprising two or more of them.

13. A molding material, according to any one of claims 1 through 6, wherein the thermoplastic polymer or oligomer as the component [B] is an oligomer obtained by adding phenol or a phenol derivative (precursor a) and an aliphatic hydrocarbon with two double bonds (precursor b).

14. A molding material, according to claim 13, wherein the precursor b is an aliphatic hydrocarbon with 6 to 15 carbon atoms and two double bonds.

15. A molding material, according to claim 14, wherein the precursor b has one or more cyclic structure.

16. A molding material, according to claim 15, wherein the precursor b is dicyclopentadiene or monocyclic monoterpene represented by molecular formula C₁₀H₁₆.

17. A molding material, according to claim 13, wherein a composition with one molecule of the precursor b added to two molecules of the precursor a accounts for 40 wt % or more in the component [B].

18. A molding material, according to claim 13, wherein the weight average molecular weight of the component [B] is 200 to 1000.

19. A molding material, according to any one of claims 1 through 6, wherein the component [C] is nylon 6, nylon 66 or nylon 6 nylon 66 copolymer.

20. A molding material, according to any one of claims 1 through 6, wherein the thermoplastic polymer or oligomer as the component [B] is an oligomer obtained by adding phenol or a phenol derivative (precursor a) and an aliphatic hydrocarbon with two double bonds (precursor b) and the component [C] is nylon 6, nylon 66 or nylon 6 nylon 66 copolymer.

21. A molding material, according to claim 20, wherein the precursor b is an aliphatic hydrocarbon with 6 to 15 carbon atoms and with two double bonds.

22. A molding material, according to claim 21, wherein the precursor b has one or more cyclic structure.

23. A molding material, according to claim 22, wherein the precursor b is dicycopentadiene or monocyclic monoterpene represented by molecular formula C₁₀H₁₆.

24. A molding material, according to claim 20, wherein a composition with one molecule of the precursor b added to two molecules of the precursor a accounts for 40 wt % or more in the component [B].

25. A molding material, according to claim 20, wherein the weight average molecular weight of the component [B] is 200 to 1000.

26. A molding material, according to any one of claims 1 through 6, wherein the reinforcing fibers of the component [A] are carbon fibers.

27. A molding material, according to any one of claims 1 through 6, wherein the reinforcing fibers of the component [A] are carbon fibers of 0.05 to 0.4 in the surface chemical function (O/C) as the ratio of the number of oxygen (O) atoms to that of carbon (C) atoms of the fiber surfaces measured by the X-ray photoelectron spectroscopy.

28. A process for producing the molding material stated in any one of claims 1, 3 and 5, comprising the steps of impregnating the component [A] with the component [B] heated and molten to have a viscosity of 100 poises or less, to form a composite;

arranging the component [C] molten to have a viscosity of 500 poises of more, to contact the composite; and

cooling the entire material to room temperature.

29. A process for producing the molding material stated in any one of claims 2, 4 or 6, comprising the steps of impregnating the component [A] with the component [b] heated and molten to have a viscosity of 100 poises or less, to form a composite;

arranging the component [C] molten to have a viscosity of 500 poises or more, to contact the composite;

cooling the entire material to room temperature; and

cutting at a length of 1 to 50 mm.

37. A fiber reinforced polyamide based resin composition, comprising 100 parts by weight of the polyamide based resin composition stated in any one of claims 30 through 33 and 5 to 200 parts by weight of reinforcing fibers.

40. A molded product, obtained by molding the molding material stated in any one of claims 1 through 6.

42. Pellets to be injection-molded, comprising the molding material stated in any one of claims 2, 4 and 6.

43. A molded product, obtained by injection-molding the pellets to be injection-molded stated in claim 42.

30. A polyamide based resin composition, comprising at least the following components [D] and [E], with the component [D] contained by 0.5 to 40 parts by weight against 100 parts by weight in total of the resin composition.

[D] An oligomer obtained by condensation of phenol or a phenol derivative (precursor a) and an aliphatic hydrocarbon with two double bonds (precursor b)

[E] A polyamide resin

31. A polyamide based resin composition, according to claim 30, wherein the precursor b is an aliphatic hydrocarbon with 6 to 15 carbon atoms and with two double bonds.

32. A molding material, according to claim 31, wherein the precursor b has one or more cyclic structure.

33. A molding material, according to claim 32, wherein the precursor b is dicyclopentadiene or monocyclic monoterpene represented by molecular formula C₁₀H₁₆.

34. A molding material, according to any one of claims 30 through 33, wherein a composition with one molecule of the precursor b added to two molecules of the precursor a accounts for 40 wt % or more in the component [D].

35. A molding material, according to any one of claims 30 through 33, wherein the weight average molecular weight of the component [D] is 200 to 1000.

36. A molding material, according to any one of claims 30 through 33, wherein the component [E] is nylon 6, nylon 66 or nylon 6 nylon 66 copolymer.

38. A fiber reinforced polyamide based resin composition, according to claim 37, wherein the reinforcing fibers are carbon fibers.

39. A fiber reinforced polyamide based resin composition, according to claim 38, wherein the rein forcing fibers are carbon fibers of 0.05 to 0.4 in the oxygen content O/C on the fiber surfaces measured by the X-ray photoelectron spectroscopy.

41. A molded product, obtained by molding the polyamide based resin composition stated in any one of claims 30 through 33.

44. Pellets to be injection-molded, comprising the polyamide based resin composition stated in any one of claims 30 through 33.

45. A molded product, obtained by injection-molding the pellets to be injection-molded stated in claim 44.