US4923734A — Laminates of polynorbornene and polyolefins deriv…

Claim 1

Independent Claim 131 words

A printed wiring board produced by a process comprising: (a) providing a dipping solution comprising polynorbornene polymers dissolved within a solvent; (b) impregnating a non-cellulosic cloth with the dipping solution and drying the impregnated cloth to remove a substantial portion of solvent to form a substrate layer; (c) pretreating the surface of a conductive film with a solution of a silane compound suitable for increasing the bond strength between the substrate layer and the conductive film layer; and (d) sandwiching an laminating a layer of polyolefin film derived from C 2 -C 4 monomer on the pretreated surface between the substrate layer and the copper layer at a temperature above the glass transition temperature of the polynorbornene and, when a curing agent is present, sufficiently high to activate said curing agent.

Claim 2

Dependent Claim 131 words

A printed wiring board produced by a process comprising: (a) providing a dipping solution comprising polynorbornene polymers dissolved within a solvent; (b) impregnating a non-cellulosic cloth with the dipping solution and drying the impregnated cloth to remove a substantial portion of solvent to form a substrate layer; (c) pretreating the surface of a conductive film with a solution of a silane compound suitable for increasing the bond strength between the substrate layer and the conductive film layer; and (d) sandwiching an laminating a layer of polyolefin film derived from C 2 -C 4 monomer on the pretreated surface between the substrate layer and the copper layer at a temperature above the glass transition temperature of the polynorbornene and, when a curing agent is present, sufficiently high to activate said curing agent.

Claim 3

Dependent Claim 17 words

A printed wiring board of claim 1 wherein the cloth is a woven or non-woven fiberglass cloth.

Claim 4

Dependent Claim 13 words

A printed wiring board of claim 1 wherein the conductive film is copper.

Claim 5

Dependent Claim 12 words

A printed wiring board of claim 1 wherein the polyolefin is polyethylene.

Claim 6

Dependent Claim 22 words

A printed wiring board of claim 1 wherein the polynorbornene is derived from vinyl-norbornene monomer polymerized with either methyltetracyclododecene or dicyclopentadiene monomers.

Claim 7

Dependent Claim 36 words

A printed wiring board of claim 1 wherein the polynorbornenes are cross-linked with the aid of a curing agent and wherein step (b) is conducted at a temperature below the activation temperature of said curing agent.

Claim 8

Dependent Claim 15 words

A printed wiring board of claim 1 wherein the dipping solution further comprises an antioxidant.

Claim 9

Dependent Claim 36 words

A printed wiring board of claim 1 wherein the copper film is the surface layer of a metallic film selected from the group consisting of copper, nickel, silver, gold, aluminum, platinum, titanium, zinc, bronze and chromium.

Claim 10

Dependent Claim 34 words

A printed wiring board of claim 1 wherein the silane suitable for increasing the bonding strength is selected from the group consisting of 3-methylacryloyloxypropyltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride, 3-(N-allyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride, N-(styrylmethyl)-3-aminopropyltrimethoxysilane hydrochloride, N-2-aminoethyl-3-aminopropyltrimethoxysilane, and 3-(N-benzyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride.

Claim 11

Dependent Claim 22 words

A printed wiring board of claim 1 wherein then non-cellulosic cloth comprises glass fibers and is pretreated with a styryl diamino silane.

Claim 12

Dependent Claim 32 words

A printed circuit wiring board of claim 1, which exhibits a peel strength of at least about 6 lbs/inch, a dielectric constant below about 3.5 and a dissipation faction of less 0.005.

Claim 13

Dependent Claim 32 words

A printed circuit wiring board of claim 1, which exhibits a peel strength of at least about 6 lbs/inch, a dielectric constant below about 3.1 and a dissipation faction of less 0.003.

Claim 14

Dependent Claim 66 words

A laminate comprising at least one substrate layer comprising a non-cellulosic cloth which has been impregnated with polynorbornene polymers laminated to at least one layer of conductive film which conductive film has been pretreated on at least one surface thereof with a silane compound suitable for increasing the bond strength between the substrate layer and the copper film layer, with a layer of polyolefin sandwiched therebetween.

Claim 15

Dependent Claim 66 words

A laminate comprising at least one substrate layer comprising a non-cellulosic cloth which has been impregnated with polynorbornene polymers laminated to at least one layer of conductive film which conductive film has been pretreated on at least one surface thereof with a silane compound suitable for increasing the bond strength between the substrate layer and the copper film layer, with a layer of polyolefin sandwiched therebetween.

Claim 16

Dependent Claim 25 words

A laminate of claim 13 wherein the conductive film is copper and the surface of the copper film which is pretreated has a bronze coating.

Claim 17

Dependent Claim 24 words

A laminate of claim 13 wherein the polynorbornene polymer is unsaturated and is derived from a cycloolefin monomer selected from methyltetracyclododecene, vinyl-norbornene and dicyclopentadiene.

Claim 18

Dependent Claim 29 words

A laminate of claim 13 wherein the monomers of the polynorbornene polymer are comprised in a weight to weight ratio of about 50-75 percent methyltetracyclododecene to 25-50 percent vinyl-norbornene.

Claim 19

Dependent Claim 29 words

A laminate of claim 13 wherein the monomers of the polynorbornene polymer are comprised in weight to weight ratio of about 75-90 percent dicyclopentadiene to about 10-25 percent vinyl-norbornene.

Claim 20

Dependent Claim 18 words

A laminate of claim 13 wherein the dipping solution further comprises a curing agent which initiates radical cross-linking.

Claim 21

Dependent Claim 27 words

A laminate of claim 13 wherein the silane is selected from the group consisting of 3-methylacryloyloxypropyltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride, 3-(N-allyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride, N-(styrylmethyl)-3-aminopropyltrimethoxysilane hydrochloride, N-2-aminoethyl-3-aminopropyltrimethoxysilane, and 3-(N-benzyl-2-aminoethylamino)-propyltrimethoxy silane hydrochloride.

Claim 22

Dependent Claim 26 words

A laminate of claim 13 further comprising placing two or more substrate layers in a stacking sequence with copper layers at the outside of the stack.

Claim 23

Dependent Claim 16 words

A laminate of claim 20 wherein a sheet of polyolefin is sandwiched between the substrate layers.

Claim 24

Dependent Claim 19 words

A laminate of claim 13 wherein the cloth is impregnated with from 30% to 80% by weight polynorbornene polymer.

Claim 25

Dependent Claim 24 words

A laminate of claim 13 wherein the thickness of the polyolefin sheet, prior to lamination, is less than or equal to about 10 mils.

Claim 26

Dependent Claim 24 words

A laminate of claim 23 wherein the thickness of the polyolefin sheet, prior to lamination, is less than or equal to about 5 mils.

Claim 27

Dependent Claim 24 words

A laminate of claim 24 wherein the thickness of the polyolefin sheet, prior to lamination, is less than or equal to about 1.5 mils.

Claim 28

Dependent Claim 10 words

A laminate of claim 13 wherein the polyolefin is polyethylene.

Claim 29

Dependent Claim 135 words

A process for producing a laminate, comprising: (a) providing a dipping solution comprised of polynorbornene polymers dissolved within a solvent; (b) impregnating an on-cellulosic cloth with the dipping solution and drying the impregnated cloth to remove a substantial portion of solvent to form a prepreg to function as a substrate layer; (c) pretreating the surface of a conductive film with a solution of a silane compound suitable for increasing the bond strength between the substrate layer and the conductive film layer; and (d) sandwiching and laminating a layer of polyolefin film derived from C 2 -C 4 monomers on the pretreated surface between the substrate layer and the copper layer, at a temperature above the glass transition temperature of the polynorbornene and, when a curing agent is present, sufficiently high to activate said curing agent.

Claim 30

Dependent Claim 135 words

A process for producing a laminate, comprising: (a) providing a dipping solution comprised of polynorbornene polymers dissolved within a solvent; (b) impregnating an on-cellulosic cloth with the dipping solution and drying the impregnated cloth to remove a substantial portion of solvent to form a prepreg to function as a substrate layer; (c) pretreating the surface of a conductive film with a solution of a silane compound suitable for increasing the bond strength between the substrate layer and the conductive film layer; and (d) sandwiching and laminating a layer of polyolefin film derived from C 2 -C 4 monomers on the pretreated surface between the substrate layer and the copper layer, at a temperature above the glass transition temperature of the polynorbornene and, when a curing agent is present, sufficiently high to activate said curing agent.

Claim 31

Dependent Claim 25 words

A process of claim 27 wherein the conductive film is copper and the surface of the copper film which is pretreated has a bronze coating.

Claim 32

Dependent Claim 24 words

A process of claim 27 wherein the polynorbornene polymer is unsaturated and is derived from a cycloolefin monomer selected from methyltetracyclododecene, vinyl-norbornene and dicyclopentadiene.

Claim 33

Dependent Claim 29 words

A process of claim 27 wherein the monomers of the polynorbornene polymer are comprised in a weight to weight ratio of about 50-75 percent methyltetracyclododecene to 25-50 percent vinyl-norbornene.

Claim 34

Dependent Claim 29 words

A process of claim 27 wherein the monomers of the polynorbornene polymer are comprised in weight to weight ratio of about 75-90 percent dicyclopentadiene to about 10-25 percent vinyl-norbornene.

Claim 35

Dependent Claim 35 words

A process of claim 27 wherein the dipping solution further comprises a curing agent which initiates radical cross-linking and wherein step (b) is conducted at a temperature below the activation temperature of said curing agent.

Claim 36

Dependent Claim 27 words

A process of claim 27 wherein the silane is selected from the group consisting of 3-methylacryloyloxypropyltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride, 3-(N-allyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride, N-(styrylmethyl)-3-aminopropyltrimethoxysilane hydrochloride, N-2-aminoethyl-3-aminopropyltrimethoxysilane, and 3-(N-benzyl-2-aminoethylamino)-propyltrimethoxy silane hydrochloride.

Claim 37

Dependent Claim 21 words

A process of claim 27 wherein the lamination is performed at a temperature above the glass transition temperature of the polynorbornene.

Claim 38

Dependent Claim 31 words

A process of claim 27 wherein the lamination is performed at temperatures between about ambient and about 250° C. and at a pressure of from about 1000 to about 1100 SI.

Claim 39

Dependent Claim 26 words

A process of claim 27 further comprising placing two or more substrate layers in a stacking sequence with copper layers at the outside of the stack.

Claim 40

Dependent Claim 16 words

A process of claim 36 wherein a sheet of polyolefin is sandwiched between the substrate layers.

Claim 41

Dependent Claim 19 words

A process of claim 27 wherein the cloth is impregnated with from 30% to 80% by weight polynorbornene polymer.

Claim 42

Dependent Claim 24 words

A process of claim 27 wherein the thickness of the polyolefin sheet, prior to lamination, is less than or equal to about 10 mils.

Claim 43

Dependent Claim 24 words

A process of claim 39 wherein the thickness of the polyolefin sheet, prior to lamination, is less than or equal to about 5 mils.

Claim 44

Dependent Claim 24 words

A process of claim 40 wherein the thickness of the polyolefin sheet, prior to lamination, is less than or equal to about 1.5 mils.

Claim 45

Dependent Claim 10 words

A process of claim 27 wherein the polyolefin is polyethylene.

Claim 46

Dependent Claim 120 words

A process of claim 27 further comprising the steps of: (e) exposing the surface of the copper layer of step (d) to photoresist imaging conditions and etching the copper layer to form a copper pattern on the surface of the laminate; (f) repeating steps (b) and (c) to produce a prepreg layer and a treated film layer; (g) arranging the pattern laminate from step (e), one or more prepreg layers and treated film layer from step (f) in the sequence laminate/prepreg layer(s)/copper film layer, optionally with a layer of polyolefin derived from a C 2 -C 4 monomer between the laminate/prepreg layer(s) and optionally between the prepreg layer(s)/and the copper film layer; and (h) laminating the sequence of step (g).

Claim 47

Dependent Claim 18 words

A process of claim 43 wherein the copper-patterned surface of step (e) is oxidized with an oxidizing agent.

Claim 48

Dependent Claim 148 words

A process for producing a laminate, comprising: (a) providing a solution comprised of polynorbornene polymers selected from copolymers comprising, in a weight-to-weight ratio of about (i) 50-75% methyltetracyclododecene 25-50% vinyl-norbornene or (ii) about 75-90% dicyclopentadiene: about 10-25% vinyl-norbornene; (b) impregnating a non-cellulosic cloth with the dipping solution; (c) drying the impregnated cloth to remove a substantial portion of solvent to form a substrate layer; (d) pretreating the surface of a conductive film with a solution of a silane compound suitable for increasing the bond strength between the substrate layer and the copper film layer; and (e) sandwiching and laminating a layer of polyolefin film derived from C 2 -C 4 monomers on the pretreated surface between the substrate layer and the conductive layer at a temperature above the glass transition temperature of the polynorbornene and, where a curing agent is present, sufficiently high to activate said curing agent.

Claim 49

Dependent Claim 148 words

A process for producing a laminate, comprising: (a) providing a solution comprised of polynorbornene polymers selected from copolymers comprising, in a weight-to-weight ratio of about (i) 50-75% methyltetracyclododecene 25-50% vinyl-norbornene or (ii) about 75-90% dicyclopentadiene: about 10-25% vinyl-norbornene; (b) impregnating a non-cellulosic cloth with the dipping solution; (c) drying the impregnated cloth to remove a substantial portion of solvent to form a substrate layer; (d) pretreating the surface of a conductive film with a solution of a silane compound suitable for increasing the bond strength between the substrate layer and the copper film layer; and (e) sandwiching and laminating a layer of polyolefin film derived from C 2 -C 4 monomers on the pretreated surface between the substrate layer and the conductive layer at a temperature above the glass transition temperature of the polynorbornene and, where a curing agent is present, sufficiently high to activate said curing agent.

Claim 50

Dependent Claim 12 words

A printed circuit wiring board prepared by the process of claim 45.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1993-05-07	1993-11-06	1994-05-08	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1997-05-07	1997-11-06	1998-05-08	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2001-05-07	2001-11-06	2002-05-08	$7700.00	Window Closed / Lapsed

Laminates of polynorbornene and polyolefins derived from C2 -C4 monomers

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