Layered product, electromagnetic-shielding molded object, and processes for producing these

• US 20060110599A1
• Filed: 12/25/2003
• Published: 05/25/2006
• Est. Priority Date: 12/27/2002
• Status: Active Grant

• Current Assignee: Toray Industries Incorporated
• Original Assignee: Toray Industries Incorporated
• Inventors: Honma, Masato, Takebe, Yoshiki, Nishizawa, Takeshi, Hasegawa, Takashi, Obara, Haruo, Eto, Seichiro, Ishibashi, Souichi, Shiho, Kosuke, Tanisugi, Hideaki
• Granted Patent: US 8,092,897 B2
• Time in Patent Office: Days
• US Class Current: 428/413
• CPC Class Codes: B29C 65/02 by heating, with or without pressure
• CPC Class Codes: B29C 65/08 using ultrasonic vibrations non-plastics element to plastics elements B29C65/645
• CPC Class Codes: B29C 65/16 Laser beams
• CPC Class Codes: B29C 65/4815 Hot melt adhesives, e.g. thermoplastic adhesives
• CPC Class Codes: B29C 65/5057 positioned between the surfaces to be joined B29C65/5035 takes precedence
• CPC Class Codes: B29C 65/8215 Tensile tests
• CPC Class Codes: B29C 66/0242 Heating, or preheating, e.g. drying B29C66/3464 takes precedence
• CPC Class Codes: B29C 66/1122 Single lap to lap joints, i.e. overlap joints B29C66/45, B29C66/472, B29C66/52272 take precedence
• CPC Class Codes: B29C 66/30322 in the form of rugosity
• CPC Class Codes: B29C 66/3034 making use of additional elements, e.g. meshes
• CPC Class Codes: B29C 66/43 Joining a relatively small portion of the surface of said articles B29C66/45 takes precedence
• CPC Class Codes: B29C 66/71 characterised by the composition of the plastics material of the parts to be joined welding bar compositions B29C65/125
• CPC Class Codes: B29C 66/7212 characterised by the composition of the fibres
• CPC Class Codes: B29C 66/72141 Fibres of continuous length
• CPC Class Codes: B29C 66/73115 Melting point
• CPC Class Codes: B29C 66/73117 Tg, i.e. glass transition temperature
• CPC Class Codes: B29C 66/73161 Roughness or rugosity
• CPC Class Codes: B29C 66/73752 the to-be-joined areas of both parts to be joined being uncured
• CPC Class Codes: B29C 66/7392 characterised by the material of at least one of the parts being a thermoplastic
• CPC Class Codes: B29C 66/7394 characterised by the material of at least one of the parts being a thermoset
• CPC Class Codes: B29C 66/73941 : characterised by the materials of both parts being thermosets
• CPC Class Codes: B29C 66/742 : to metals or their alloys
• CPC Class Codes: B29C 66/7422 : Aluminium or alloys of aluminium
• CPC Class Codes: B29C 66/74283 : Iron or alloys of iron, e.g. steel
• CPC Class Codes: B29C 66/8322 : Joining or pressing tools reciprocating along one axis
• CPC Class Codes: B29C 66/91445 : by steps
• CPC Class Codes: B29C 66/919 : characterised by specific temperature, heat or thermal flux values or ranges specific electrical resistance values B29C66/81262
• CPC Class Codes: B29C 66/91921 : in explicit relation to another temperature, e.g. to the softening temperature or softening point, to the thermal degradation temperature or to the ambient temperature
• CPC Class Codes: B29C 66/91933 : higher than said fusion temperature
• CPC Class Codes: B29C 66/91935 : lower than said fusion temperature
• CPC Class Codes: B29C 66/91943 : higher than said glass transition temperature
• CPC Class Codes: B29C 66/929 : characterized by specific pressure, force, mechanical power or displacement values or ranges
• CPC Class Codes: B29C 66/949 : characterised by specific time values or ranges
• CPC Class Codes: B29C 70/0035 : comprising two or more matrix materials
• CPC Class Codes: B29K 2023/00 : Use of polyalkenes or derivatives thereof as moulding material
• CPC Class Codes: B29K 2023/083 : EVA, i.e. ethylene vinyl acetate copolymer
• CPC Class Codes: B29K 2025/04 : Polymers of styrene
• CPC Class Codes: B29K 2033/08 : Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate
• CPC Class Codes: B29K 2063/00 : Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2067/00 : Use of polyesters or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2069/00 : Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2075/00 : Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2077/00 : Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2081/04 : Polysulfides, e.g. PPS, i.e. polyphenylene sulfide or derivatives thereof
• CPC Class Codes: B29K 2307/04 : Carbon
• CPC Class Codes: B29L 2031/7172 : Fuel tanks, jerry cans
• CPC Class Codes: B32B 2260/021 : Fibrous or filamentary layer
• CPC Class Codes: B32B 2260/046 : Synthetic resin
• CPC Class Codes: B32B 2262/106 : Carbon fibres, e.g. graphite fibres
• CPC Class Codes: B32B 2305/08 : Reinforcements
• CPC Class Codes: B32B 2457/00 : Electrical equipment
• CPC Class Codes: B32B 2535/00 : Medical equipment, e.g. bandage, prostheses or catheter
• CPC Class Codes: B32B 2605/00 : Vehicles
• CPC Class Codes: B32B 27/04 : as impregnant, bonding, or embedding substance not used
• CPC Class Codes: B32B 5/022 : Non-woven fabric
• CPC Class Codes: B32B 5/10 : characterised by a fibrous or filamentary layer reinforced with filaments
• CPC Class Codes: B32B 5/24 : one layer being a fibrous or filamentary layer
• CPC Class Codes: B32B 5/26 : another layer next to it also being fibrous or filamentary relative arrangement of fibres or filaments of different layers B32B5/12
• CPC Class Codes: B60K 15/03177 : made of non-metallic material, e.g. plastics, or of a combination of non-metallic and metallic material B60K15/03006 takes precedence
• CPC Class Codes: B60K 2015/03046 : made from more than one layer
• CPC Class Codes: H05K 9/009 : comprising electro-conductive fibres, e.g. metal fibres, carbon fibres, metallised textile fibres, electro-conductive mesh, woven, non-woven mat, fleece, cross-linked
• CPC Class Codes: Y10T 428/24364 : with transparent or protective coating
• CPC Class Codes: Y10T 428/249924 : Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
• CPC Class Codes: Y10T 428/249942 : Fibers are aligned substantially parallel
• CPC Class Codes: Y10T 428/249945 : Carbon or carbonaceous fiber
• 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 428/2826 : Synthetic resin or polymer
• CPC Class Codes: Y10T 428/2896 : including nitrogen containing condensation polymer [e.g., polyurethane, polyisocyanate, etc.]
• CPC Class Codes: Y10T 428/31504 : Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31507 : Of polycarbonate
• CPC Class Codes: Y10T 428/31511 : Of epoxy ether
• CPC Class Codes: Y10T 428/31551 : Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• CPC Class Codes: Y10T 428/31725 : Of polyamide
• CPC Class Codes: Y10T 428/31739 : Nylon type
• CPC Class Codes: Y10T 428/31786 : Of polyester [e.g., alkyd, etc.]
• CPC Class Codes: Y10T 428/31855 : Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31935 : Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31938 : Polymer of monoethylenically unsaturated hydrocarbon

Abstract

A layered product which is a molded object comprising a thermoset resin layer, a thermoplastic resin layer, and reinforcing fibers comprising many continuous filaments, wherein the thremoset resin layer has been united with the thermoplastic resin layer at the interface between these layers, the resin of the thermoset resin layer and the resin of the thermoplastic resin layer each having an irregular surface shape at the interface, and a group of filaments among the reinforcing fibers are in contact with at least the resin of the thermoset resin layer and the other group of filaments among the reinforcing fibers are in contact with at least the resin of the thermoplastic resin layer, that side of the thermoplastic resin layer which is opposite to the interface being a surface of the molded object.

Claims

1. A layered product as a molded object comprising a thermosetting resin layer, a thermoplastic resin layer and groups of reinforcing fibers consisting of numerous continuous filaments, wherein said thermosetting resin layer and said thermoplastic resin layer are integrated at the interface between these layers in such a manner that the resin of said thermosetting resin layer and the resin of said thermoplastic resin layer are formed to be rugged at the interface;

a set of filaments among said groups of reinforcing fibers is kept in contact with at least the resin of said thermosetting resin layer while the other set of filaments among said groups of reinforcing fibers is kept in contact with at least the resin of said thermoplastic resin layer; and

the face of said thermoplastic resin layer opposite to said interface is positioned on the surface of said molded object.

2. A layered product, according to claim 1, wherein said numerous continuous filaments are arranged in one direction, and the interface between said thermosetting resin layer and said thermoplastic resin layer exists among said groups of reinforcing fibers.

3. A layered product, according to claim 1, wherein the glass transition temperature of the resin forming said thermosetting resin layer is 60°

C. or higher.

4. A layered product, according to claim 1, wherein in said thermoplastic resin layer, the maximum thickness of the area where said continuous filaments exist is 10 μ

m or more.

5. A layered product, according to claim 4, wherein said maximum thickness is 1,000 μ

m or less.

6. A layered product, according to claim 1, wherein the surface area of said thermoplastic resin layer accounts for 0.1 to 50% of the surface area of the layered product.

7. A layered product, according to claim 1, wherein a layer having the same structure as that formed of said thermosetting resin, said thermoplastic resin and groups of reinforcing fibers consisting of numerous continuous filaments is formed on the face of the layered product on the side opposite to the side where said thermoplastic resin layer is positioned.

8. A layered product, according to claim 1, wherein the bonding strength of the test piece of the layered product defined in the specification based on ISO4587 is 6 MPa or higher at room temperature.

11. A layered product, according to claim 1 or 9, wherein the numerous continuous filaments constituting said groups of reinforcing fibers are carbon fibers.

12. A layered product, according to claim 1 or 9, wherein said thermosetting resin is a resin mainly composed of an epoxy resin.

13. A layered product, according to claim 1 or 9, wherein said thermoplastic resin is at least one resin selected from a group consisting of polyamide-based resins, polyester-based resins, polycarbonate-based resins, styrene-based resins, EVA resin, urethane-based resins, acrylic resins, polyolefin-based resins and PPS-based resins.

14. A process for producing a layered product as set forth in claim 1 or 9, comprising the steps of disposing a base material for thermal bonding composed of a thermoplastic resin, on a surface of a prepreg obtained by impregnating groups of reinforcing fibers consisting of numerous continuous filaments with a thermosetting resin not yet set, and impregnating said groups of reinforcing fibers with the thermoplastic resin of said base material for thermal bonding, during the setting reaction of said thermosetting resin or during preheating before the setting reaction.

15. A process for producing a layered product, according to claim 14, wherein a pressing pressure of 0.1 MPa or higher is caused to act when said groups of reinforcing fibers are impregnated with the thermoplastic resin.

16. An integrated molded object which comprises a first member composed of a layered product as set forth in claim 1 or 9 and a second member composed of another structural member, wherein the first member and the second member are bonded to each other through said thermoplastic resin in said first member.

17. An integrated molded object, according to claim 16, wherein said second member is at least one member selected from the group consisting of a member composed of a layered product comprising (1) a thermosetting resin layer, a thermoplastic resin layer and groups of reinforcing fibers consisting of numerous continuous filaments, wherein said thermosetting resin layer and said thermoplastic resin layer are integrated at the interface between these layers in such a manner that the resin of said thermosetting resin layer and the resin of said thermoplastic resin layer are formed to be rugged at the interface;

a set of filaments among said groups of reinforcing fibers is kept in contact with at least the resin of said thermosetting resin layer while the other set of filaments among said groups of reinforcing fibers is kept in contact with at least the resin of said thermoplastic resin layer; and

the face of said thermoplastic resin layer opposite to said interface is positioned on the surface of said molded object, or (2) a thermosetting resin composition having groups of reinforcing fibers consisting of numerous continuous filaments arranged in a thermosetting matrix resin and a film composed of a thermoplastic resin composition formed at least on a portion of the surface of said thermosetting resin composition, wherein the normal bonding strength defined in the specification between the layered product and another molded object bonded through said film is 10 MPa or higher at a temperature of 40°

C. and lower than 10 MPa at a temperature of 140°

C.;

a member composed of a thermoplastic resin composition and a member composed of a metallic material.

18. A process for producing an integrated molded object as set forth in claim 16, comprising the step of integrating said first member and said second member with each other, by at least one integration method selected from the group consisting of thermal welding, vibration welding, ultrasonic welding, laser welding, insert injection molding and outsert injection molding.

19. An integrated molded object, according to claim 16, which is a part member or a housing of an electric or electronic apparatus, an office automation apparatus, a household electric appliance or a medical apparatus.

20. An integrated molded object, according to claim 16, which is a part member or a panel of a motor vehicle, a two-wheeler, a bicycle, an aircraft or an architecture.

26. A process for producing a layered product, according to claim 14, wherein said base material for thermal bonding is a base material for thermal bonding comprising adhering members of identical and/or different kinds, wherein the bonding strength (S) of the test piece of the layered product defined in the specification based on ISO4587 is 5.0 MPa or higher at a temperature of 100°

C. and 1.0 MPa or lower at a temperature of 200°

C.

9. A layered product, comprising a thermosetting resin composition having groups of reinforcing fibers consisting of numerous continuous filaments arranged in a thermosetting matrix resin and a film composed of a thermoplastic resin composition formed at least on a portion of the surface of said thermosetting resin composition, wherein the normal bonding strength defined in the specification between the layered product and another molded object bonded through said film is 10 MPa or higher at a temperature of 40°

C. and lower than 10 MPa at a temperature of 140°

C.

10. A layered product, according to claim 9, wherein the average thickness of said film composed of a thermoplastic resin composition is from 0.1 to 1,000 μ

m.

21. A base material for thermal bonding of adhering members of identical and/or different kinds, wherein the bonding strength (S) of the test piece of the layered product defined in the specification based on ISO4587 is 5.0 MPa or higher at a temperature of 100°

C. and 1.0 MPa or lower at a temperature of 200°

C.

22. A base material for thermal bonding, according to claim 21, wherein where the bonding strength at a temperature t (°

C.) is St (MPa) and the bonding strength at a temperature (t+30) (°

C.) is S_(t+30) (MPa), the temperature t satisfying the relation of St≧

3×

S_(t+30) is from 100°

C. to 200°

C.

23. A base material for thermal bonding, according to claim 21, wherein said base material is composed of a copolyamide-based resin composition.

24. A base material for thermal bonding, according to claim 23, wherein said copolyamide contains ternary copolyamide 6/66/610 as a component.

25. A base material for thermal bonding, according to claim 21, wherein said base material is in a form of a nonwoven fabric or film having a unit weight of 1 to 100 g/m².

27. An electromagnetic-shielding molded object, obtained by integrating a first structural member composed of a resin composition having groups of conductive fibers consisting of numerous continuous filaments arranged therein and a second structural member composed of a thermoplastic resin composition, wherein the electromagnetic shielding property of said first structural member at a frequency of 1 GHz measured according to the KEC method is 40 dB or more.

28. An electromagnetic-shielding molded object, according to claim 27, wherein said first structural member is a layered product comprising (1) a thermosetting resin layer, a thermoplastic resin layer and groups of reinforcing fibers consisting of numerous continuous filaments, wherein said thermosetting resin layer and said thermoplastic resin layer are integrated at the interface between these layers in such a manner that the resin of said thermosetting resin layer and the resin of said thermoplastic resin layer are formed to be rugged at the interface;

a set of filaments among said groups of reinforcing fibers is kept in contact with at least the resin of said thermosetting resin layer while the other set of filaments among said groups of reinforcing fibers is kept in contact with at least the resin of said thermoplastic resin layer; and

the face of said thermoplastic resin layer opposite to said interface is positioned on the surface of said molded object, or (2) a thermosetting resin composition having groups of reinforcing fibers consisting of numerous continuous filaments arranged in a thermosetting matrix resin and a film composed of a thermoplastic resin composition formed at least on a portion of the surface of said thermosetting resin composition, wherein the normal bonding strength defined in the specification between the layered product and another molded object bonded through said film is 10 MPa or higher at a temperature of 40°

C. and lower than 10 MPa at a temperature of 140°

C.; and

wherein the numerous continuous filaments constituting said groups of reinforcing fibers are carbon fibers.

29. An electromagnetic-shielding molded object, according to claim 27, wherein the flexural modulus of said first structural member based on ASTM D790 is 8 GPa or more as the test, piece defined in the specification.

30. An electromagnetic-shielding molded object, according to claim 27, wherein the average thickness of said first structural member is 1.6 mm or less.

31. An electromagnetic-shielding molded object, according to claim 27, wherein when the molded object is observed from outside, a pattern based on an arranged state of said numerous continuous filaments can be observed.

32. An electromagnetic-shielding molded object, according to claim 27, wherein the resin composition in said first structural member is a thermosetting resin.

33. An electromagnetic-shielding molded object, according to claim 27, wherein the resin composition in said first structural member is a thermoplastic resin.

34. An electromagnetic-shielding molded object, according to claim 27, wherein the thermoplastic resin composition of said second structural member contains discontinuous carbon fibers;

the weight average fiber length Lw of said carbon fibers is 0.4 mm or more; and

the ratio Lw/Ln of the weight average fiber length Lw to the number average fiber length Ln is from 1.3 to 2.0.

37. A process for producing an electromagnetic-shielding molded object as set forth in claim 27, comprising a first step of inserting a first structural member produced by molding beforehand, into a mold and a second step of injecting a thermoplastic resin composition to form a second structural member, to the first structural member inserted in said mold, for integrating said second structural member with said first structural member.

38. A process for producing an electromagnetic-shielding molded object as set forth in claim 27, comprising the step of integrating a first structural member produced by molding beforehand and a second structural member produced by injection molding beforehand, by means of ultrasonic welding.

35. An electromagnetic-shielding molded object, which is a part member or a housing of an electric or electronic apparatus, an office automation apparatus, a household electric appliance or a medical apparatus.

36. An electromagnetic-shielding molded object, according to claim 35, wherein said first structural member is positioned at least at a portion of a top face portion of said housing, and said second structural member is positioned at a member including any one or more of a frame, boss, rib, hinge and runner of said housing.