Molding material and production process

• US 6,455,143 B1
• Filed: 07/15/1998
• Issued: 09/24/2002
• Est. Priority Date: 11/06/1996
• Status: Expired due to Term

• Current Assignee: Toray Industries Incorporated
• Original Assignee: Toray Industries Incorporated
• Inventors: Ishibashi, Soichi, Kyono, Tetsuyuki
• Primary Examiner(s): Cole, Elizabeth M.
• Assistant Examiner(s): SINGH-PANDEY, ARTI R
• Application Number:
  US09/101,251
• Time in Patent Office: 1,532 Days
• Field of Search: 428/300.7, 428/301.4, 428/300.1, 428/297.4, 428/373, 428/375, 428/376, 428/377, 428/397, 428/293.4, 428/294.1, 428/296.4, 428/296.7, 428/297.1, 428/368, 428/370
• US Class Current: 428/294.1
• 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

A molding material comprises at least the following components A, B and C, with the component C arranged to contact a composite comprising the components A plus B. The components are elongated members identified as:

A A continuous reinforcing fiber bundle,

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

C A thermoplastic resin having a weight average molecular weight of 10,000 or more.

Claims

1. A molding material comprising a composite A+B contacted to a component C, said composite comprising a continuous reinforcing fiber bundle A dispersed in a thermoplastic polymer B or oligomer B having a weight average molecular weight of 200 to 50,000 and a thermoplastic resin C intimately adhered to said composite A+B;

wherein said resin C has a predetermined melt viscosity and a weight average molecular weight of 10,000 or more, and wherein said thermoplastic polymer B or oligomer B has a melt viscosity that is lower than said melt viscosity of said thermoplastic resin C.

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

3. A process for producing the molding material stated in any one of claims 2, comprising the steps of impregnating said continuous reinforcing fiber bundle A with said thermoplastic polymer B or oligomer B heated and molten to a viscosity of 100 poises or less, to form composite A+B;

arranging said component C in molten condition having a viscosity of 500 poises or more, causing said component C to contact said composite A+B;

cooling the resulting material to room temperature; and

cutting the product to a length of 1 to 50 mm.

4. A molding material, according to claim 1, wherein the component C is arranged to surroundingly cover said composite A+B.

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

6. Pellets to be injection-molded, comprising the molding material stated in any one of claims 2 and 5.

7. A molded product, obtained by injection-molding the pellets to be injection-molded stated in claim 6.

8. Pellets to be injection-molded, comprising the polyamide based resin composition stated in claim 6.

9. A molded product, obtained by injection-molding the pellets to be injection-molded stated in claim 8.

10. A molding material, according to claim 1, wherein the component C is arranged as a layer attached to said composite A+B.

11. A molding material, according to claim 10, wherein the molding material is cut to a length of 1 to 50 mm.

12. A molding material, according to claim 1, wherein the melt viscosity of the thermoplastic polymer B or oligomer is 100 poises or less, and the melt viscosity of the component is 500 poises or more.

13. A molding material, according to claim 1, wherein the absolute value of the difference between the solubility parameter δ

1 of the thermoplastic polymer B or oligomer and the solubility parameter δ

2 of the component is smaller than 3.5.

14. A molding material, according to claim 1, wherein when the content of the thermoplastic polymer B or oligomer 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 when excluding the thermoplastic polymer B or oligomer B from the components of said molding material.

15. A molding material, according to claim 1, wherein the volumetric content of the said continuous reinforcing fiber bundle in the composite A+B is 40 to 95%.

16. A molding material, according to claim 1, wherein the void volume of the composite A+B is 0 to 40%.

17. A molding material, according to claim 1, wherein the component is a polyamide, polyolefin, polycarbonate, or any of the mixtures and copolymers comprising two or more of them.

18. A molding material, according to claim 1, wherein the thermoplastic polymer B or oligomer B is an oligomer obtained by adding phenol or a phenol derivative, referred to herein as precursor a, and an aliphatic hydrocarbon having two double bonds referred to herein as precursor b.

19. A molding material, according to claim 18, wherein said precursor b is an aliphatic hydrocarbon having 6 to 15 carbon atoms and two double bonds.

20. A molding material, according to claim 19, wherein said precursor b has one or more cyclic structures.

21. A molding material, according to claim 20, wherein said precursor b is dicyclopentadiene or monocyclic monoterpene represented by the molecular formula C₁₀H₁₆.

22. A molding material, according to claim 18, wherein at least 40 wt % or more of said component B comprises one molecule of said precursor b added to two molecules of said precursor a.

23. A molding material, according to claim 18, wherein the weight average molecular weight of said thermoplastic polymer B or oligomer comprises 200 to 1000.

24. A molding material, according to claim 1, wherein said component comprises nylon 6, nylon 66 or nylon 6 nylon 66 copolymer.

25. A molding material, according to claim 1, wherein the thermoplastic polymer B or oligomer component B is an oligomer obtained by adding phenol or a phenol derivative, and an aliphatic hydrocarbon with two double bonds, and wherein said component C is nylon 6, nylon 66 or nylon 6 nylon 66 copolymer.

26. A molding material, according to claim 25, wherein said aliphatic hydrocarbon with two double bonds is an aliphatic hydrocarbon having 6 to 15 carbon atoms.

27. A molding material, according to claim 26, wherein said aliphatic hydrocarbon with two double bonds has one or more cyclic structures.

28. A molding material, according to claim 27, wherein said aliphatic hydrocarbon with two double bonds is dicyclopentadiene or monocyclic monoterpene represented by the molecular formula C₁₀H₁₆.

29. A molding material, according to claim 25, wherein at least 40 wt % of said thermoplastic polymer B or oligomer B comprises a composition having one molecule of said aliphatic hydrocarbon with two double bonds added to two molecules of said phenol or phenol derivative.

30. A molding material, according to claim 25, wherein the weight average molecular weight of said thermoplastic polymer B or oligomer is 200 to 1000.

31. A molding material, according to claims 1, wherein said fibers of the said continuous reinforcing fiber bundle are carbon fibers.

32. A molding material, according to claim 1, wherein said fibers of said continuous reinforcing fiber bundle A are carbon fibers having 0.05 to 0.4 surface chemical function (O/C) comprising the ratio of the number of oxygen (O) atoms to the number of carbon (C) atoms of the fiber surfaces, as measured by X-ray photoelectron spectroscopy.

33. A process for producing a molding material defined in any one of claims 1, 4 and 10, comprising the steps of impregnating said continuous reinforcing fiber bundle A with said thermoplastic polymer B or oligomer B heated and molten to a viscosity of 100 poises or less, to form said composite A+B;

arranging said component C in molten condition having a viscosity of 500 poises or more, causing said component C to contact said composite A+B; and

cooling the resulting material to room temperature.

34. A molded product, obtained by molding the molding material stated in claim 1.

35. A molded product, obtained by molding the polyamide based resin composition stated in claim 17.