Molding material and production process

• US 6,828,374 B2
• Filed: 09/18/2001
• Issued: 12/07/2004
• Est. Priority Date: 11/06/1996
• Status: Expired due to Term

• Current Assignee: Toray Industries Incorporated
• Original Assignee: Toray Industries Incorporated
• Inventors: Kyono, Tetsuyuki, Ishibashi, Soichi
• Primary Examiner(s): Cain, Edward J.
• Application Number:
  US09/954,959
• Publication Number:
  US 20020019182A1
• Time in Patent Office: 1,176 Days
• Field of Search: 524/323, 524/326, 524/342, 524/345, 524/494, 524/495
• US Class Current: 524/495
• 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 polyamide based resin composition, comprising:

component an oligomer obtained by condensation of phenol or a phenol derivative (precursor a) and an aliphatic hydrocarbon with two double bonds (precursor b), wherein a product with one molecule of the precursor b added to two molecules of the precursor a accounts for 40 wt % or more of the component; and

component a polyamide resin;

with the component contained in an amount of 0.5 to 40 parts by weight based on 100 parts by weight of the resin composition.

2. The resin composition, according to claim 1, wherein the precursor b is an aliphatic hydrocarbon with 6 to 15 carbon atoms and with two double bonds.

3. The resin composition, according to claim 2, wherein the precursor b has one or more cyclic structures.

4. The resin composition, according to claim 3, wherein the precursor b is dicyclopentadiene or monocyclic monoterpene represented by molecular formula C₁₀H₁₆.

5. The resin composition, according to claim 1, wherein the weight average molecular weight of the component is 200 to 1000.

6. The resin composition, according to claim 1, wherein the component is selected from the group consisting of nylon 6, nylon 66 and nylon 6 nylon 66 copolymer.

7. A molding resin composition, comprising 100 parts by weight of components and as defined in claim 1 and 5 to 200 parts by weight of reinforcing fibers.

8. The molding resin composition, according to claim 7, wherein the reinforcing fibers are carbon fibers.

9. The molding resin composition, according to claim 8, wherein the reinforcing 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.

10. A method of making a polymeric composite of a fiber bundle A that has interstices between individual fibers of said bundle A, reinforced by a multiplicity of said fibers in a dispersed condition, and said composite being adapted to be molded into a useful shape,

said method comprising the steps of:

(a) dispersing the fibers of the bundle A by pressing a thermoplastic polymer or oligomer B with a force sufficient to impregnate said fibers with said polymer or oligomer B and substantially fill said interstices with said polymer or oligomer B, while expelling any air from the clearances between said individual fibers,

said polymer or oligomer B having a weight average molecular weight of 200 to 50,000,

dispersing said filaments to create clearances between the individual filaments in the matrix, which clearances are substantially filled with said thermoplastic polymer or oligomer B to form a composite A+B with said fibers substantially evenly distributed in said polymer or oligomer B, and

(b) adhering to said composite A+B a thermoplastic polymeric resin C which has a predetermined melt viscosity and a molecular weight of 10,000 or more, and wherein

said thermoplastic polymer or oligomer B has a melt viscosity that is lower than said melt viscosity of said resin C.

11. A method for making a polymeric composite for molding comprising:

(a) pressing a thermoplastic polymer or oligomer B with a force sufficient to impregnate a fiber bundle A with said polymer or oligomer B to form a composite A+B, said polymer or oligomer B having a weight average molecular weight of 200 to 50,000, and

(b) adhering a thermoplastic resin C which has a molecular weight of 10,000 or more to said composite A+B,

wherein said thermoplastic polymer or oligomer B has a melt viscosity that is lower than said melt viscosity of said resin C.

12. The method according to claim 11, wherein said thermoplastic polymer or oligomer (B) is an oligomer (D) obtained by condensation of phenol or a phenol derivative (precursor a) and an aliphatic hydrocarbon with two double bonds (precursor b) and said thermoplastic resin (C) is a polyamide based resin (E), with the component contained by 0.5 to 40 parts by weight against 100 parts by weight based on the resin composition.

13. The method according to claim 12, wherein the precursor b is an aliphatic hydrocarbon with 6 to 15 carbon atoms and with two double bonds.

14. The method according to claim 13, wherein the precursor b has one or more cyclic structure.

15. The method according to claim 14, wherein the precursor b is dicyclopentadiene or monocyclic monoterpene represented by molecular formula C₁₀H₁₆.

16. The method according to claim 12, 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.

17. The method according to claim 12, wherein the component is selected from the group consisting of nylon 6, nylon 66 or nylon 6 nylon 66 copolymer.

18. The method according to claim 11, wherein the polymeric composite comprises 5 to 200 parts by weight of reinforcing fibers based on 100 parts by weight of the thermoplastic polymer or oligomer (B) and the thermoplastic resin (C).