Laminate of fiber-reinforced, crosslinked polypropylene

• US 4,833,005 A
• Filed: 12/02/1987
• Issued: 05/23/1989
• Est. Priority Date: 12/03/1986
• Status: Expired due to Fees

• Current Assignee: Dynamit Nobel AG
• Original Assignee: Dynamit Nobel AG
• Inventors: Kuhnel, Werner, Klaar, Karlo, Spielau, Paul
• Primary Examiner(s): CANNON, JAMES
• Application Number:
  US07/127,956
• Time in Patent Office: 538 Days
• Field of Search: 428/224, 428/251, 428/252, 428/263, 428/272, 428/273, 428/285, 428/286, 428/287, 428/288, 428/290, 428/451, 428/461, 428/901, 361/397, 174/68.5, 156/228, 156/288, 156/307.7
• US Class Current: 442/376
• CPC Class Codes: B32B 15/08 of synthetic resin
• CPC Class Codes: B32B 15/14 next to a fibrous or filamentary layer
• CPC Class Codes: B32B 15/20 comprising aluminium or copper B32B15/016 and B32B15/017 take precedence
• CPC Class Codes: B32B 2262/101 Glass fibres
• CPC Class Codes: B32B 2305/08 Reinforcements
• 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: C08F 10/06 Propene
• CPC Class Codes: C08F 230/085 the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
• CPC Class Codes: C08F 255/02 on to polymers of olefins having two or three carbon atoms
• CPC Class Codes: C08F 8/42 Introducing metal atoms or metal-containing groups
• CPC Class Codes: H05K 1/024 Dielectric details, e.g. changing the dielectric material around a transmission line
• CPC Class Codes: H05K 1/032 consisting of one material
• CPC Class Codes: H05K 1/0366 reinforced, e.g. by fibres, fabrics H05K1/036 takes precedence
• CPC Class Codes: H05K 2201/0129 Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
• CPC Class Codes: H05K 2201/0145 Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]
• CPC Class Codes: H05K 2201/0158 Polyalkene or polyolefin, e.g. polyethylene [PE], polypropylene [PP]
• CPC Class Codes: H05K 2201/0239 Coupling agent for particles using a coupling agent to improve the adhesion between an insulating substrate and a metal H05K3/389
• CPC Class Codes: H05K 2201/0278 Polymeric fibers
• CPC Class Codes: Y10S 428/901 Printed circuit
• CPC Class Codes: Y10T 428/24994 Fiber embedded in or on the surface of a polymeric matrix
• CPC Class Codes: Y10T 428/249949 : Two or more chemically different fibers
• CPC Class Codes: Y10T 428/249951 : Including a free metal or alloy constituent
• CPC Class Codes: Y10T 428/31667 : Next to addition polymer from unsaturated monomers, or aldehyde or ketone condensation product
• CPC Class Codes: Y10T 428/31692 : Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 442/654 : Including a free metal or alloy constituent

Abstract

A laminate is made of textile sheet structures of synthetic fibers or glass fibers with a covering of polypropylene. The polypropylene is crosslinked by addition of crosslinking agents. The laminate has good electrical insulating properties, perfect solder bath stability, and good mechanical machinability. This laminate is provided, in heated presses, with metal layers or can be provided, in heated presses, with metal layers or can be provided with such metals layers by the application of metallic foils or by electrolytical methods, and serves for the manufacture of printed circuits and ribbon cables. An advantageous production of the textile sheet structures encased with crosslinked polypropylene can be performed on roll stands by thermoplastic encasing and smoothing in a continuous process.

Claims

1. A laminate of substrate material for printed circuits which comprises at least one fiber-reinforced support layer, said support layer having a flat structure that is formed of synthetic organic fibers and/or of glass fibers and that is penetrated by a polypropylene material containing crosslinking agent, said laminated exhibiting relative permittivity φ

r at 20°

C. and 10⁶ Hz of smaller than 3, dissipation factor tan δ

at 20°

C. and 10⁶ Hz, measured after storing for 96 hours under a climate of 40°

C. and 92% relative atmospheric humidity (DIN

     53483) of <

0.02, and a solder bath stability >

20 seconds, measured at 260°

C. (DIN IEC

     52);

said crosslinking agent comprising 1.0-5% by weight, based on the amount of polypropylene material, of an alkoxy-silane compound of the formula;

##STR2## wherein R₁ is hydrogen or an alkyl radical of 1-4 carbon atoms;

R₂ is a straight-chain alkylene radical of 1-10 carbon atoms;

R₂ is a straight-chain alkylene radical of 1-10 carbon atoms;

R₃ is an alkoxy radical of 1-5 carbon atoms which can optionally be interrupted by an oxygen atom; and

m and n are equal to 0 or 1.

2. A laminate according to claim 1, wherein the flat structure contains fibers in the form of a nonwoven mat, a woven fabric, or a mat formed of glass fibers, mineral fibers or synthetic fibers, having melting points of above 120°

C.

3. A laminate according to claim 1, wherein said at least one support layer contains, depending on the desired flexibility or rigidity, 5-60% by weight of the reinforcing fibers, based on the total weight of the laminate.

4. A laminate according to claim 2, wherein said at least one support layer contains, depending on the desired flexibility or rigidity, 5-60% by weight of the reinforcing fibers, based on the total weight of the laminate.

5. A laminate according to claim 1, wherein, for penetration of the reinforcing fibers, said polypropylene material comprises an essentially isotactic homopolymer of propylene with a density of about 0.90-0.91 g/cm³ and a melt flow index MFI (230°

C./5 kp) of smaller than 3.0 g/10 min, preferably smaller than 1.0 g/10 min, and with a molecular weight larger than 5×

10⁵.

6. A laminate according to claim 3, wherein said cross-linking agent comprises 1.0-5% by weight, based on the amount of polypropylene materials, of an alkoxy-silane compound of the formula:

##STR3## wherein R₁ is hydrogen or an alkyl radical of 1-4 carbon atoms;

R₂ is straight-chain alkylene radical of 1-10 carbon atoms;

R₃ is an alkoxy radical of 1-5 carbon atoms which can optionally be interrupted by an oxygen atom; and

m and n are equal to 0 or 1.

7. A laminate according to claim 1, wherein said cross-linking agent further comprises 0.1-0.8% by weight, based on the amount of polypropylene material, of an organic peroxide having a one-minute half-life temperature of about 160°

-240°

C.

8. A laminate according to claim 1, wherein the cross-linking agent further comprises up to 0.1% by weight of a tin compound as a silanol condensation catalyst, based on the weight of the amount of polypropylene material.

9. A laminate according to claim 1, wherein said laminate further comprises a metal foil, bonded to at least one external layer by means of an adhesion promoter.

10. A laminate according to claim 1, wherein the polypropylene material is a polypropylene homopolymer or a polyproylene copolymer containing up to 12% by weight of ethylene.

11. A laminate according to claim 1, wherein the flat structures consist of reinforcing synthetic organic fibers, linear, saturated polyesters or copolyesters.

12. A process for the production of laminates for printed circuits which comprises forming at least two flat support layers with a bilateral covering of a film of polypropylene material comprising at least one of a homopolymer and a copolymer propylene containing crosslinking agent;

and press molding the at least two layers in a heated press under a pressure of 5-200 bar into a flat structure having a thickness of 0.1-2.0 mm;

said crosslinking agent comprising 1.0-5% by weight, based on the amount of propylene material of an alkoxy-silane compound of the formula;

##STR4## wherein R₁ is hydrogen or an alkyl radical of 1-4 ccarbon atoms;

R₂ is a straight-chain alkylene radical of 1-10 carbon atoms;

R₃ is an alkoxy radical of 1-5 atoms which can optionally be interrupted by an oxygen atom; and

m and n are equal to 0 or 1.

13. A process according to claim 12, wherein the support layers are sections of continuously manufactured reinforcing sheets encased by crosslinkable or, respectively, crosslinked polypropylene.

14. A process according to claim 12, wherein the support layers, covered with polypropylene homo- or copolymer, are manufactured continuously on a cluster roll stand by introducing the polypropylene material and the crosslinking agent onto both sides of each support layer and smoothing lengths of sheeting overlying each other.

15. A process for the production of laminates according to claim 12, comprising working of polypropylene homopolymer or propylene-ethylene copolymer of up to 12% by weight of ethylene, containing 5 to 60 wt.-% of textile or fiber reinforcement, the balance of 40 to 95 wt.-% being polypropylene material, the polypropylene material having a molecular weight of higher than 5×

10⁵ and the MFI(melt flow index) (230/5) being then 0.1 to 3.0 g /10 min., the working is for 0,2 to 10 min. at 200°

to 230°

C. in the presence of 0.1 to 5.0 wt.-%, based on the amount of polypropylene material, of said alkoxy-silane of said formula and 0.1 to 0.4 wt.-%, based on polypropylene material, of one or more peroxides having a one-minute half-life temperature of about 160°

to 240°

C., effecting in the laminates degrees of crosslinking of 30 to 95%, measured by determining the insoluble portion in decahydronaphthaline, the so produced laminates becoming duroplastic and being stable in a solder bath of 260°

C. for more than 20 seconds, and providing said laminates with a conductive metal layer.