Polymerization compositions and processes having polymeric binding agents

Claim 2

A process for making a photoresist which comprises: preparing a photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of and being solely one or more non-gaseous compounds, containing at least two terminal ethylenic groups, having a boiling point above 100° C. and being selected from the group consisting of an unsaturated ester of a polyol, an unsaturated amide, and a vinyl ester; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerization inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: a first monomeric material which contains one or more non-acidic vinyl compounds selected from the group having the general formula: ##SPC2## wherein R is hydrogen, an alkyl group having from 1 to 6 carbon atoms or a halo group; and a second monomeric material which consists essentially of one or more alpha,beta-unsaturated carboxyl-containing monomers having from 3 to 15 carbon atoms; wherein the ratio of the first monomeric material to the second monomeric material is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base; exposing a portion of said photopolymerizable layer to actinic light; and washing said layer with a dilute aqueous alkaline solution to dissolve the unexposed portion of the photopolymerizable layer.

Claim 3

The process of claim 1 wherein the photopolymerizable layer is supported on a metallic substrate prior to said washing step.

Claim 4

The process of claim 1 wherein the copolymer is of styrene and an unsaturated carboxyl-containing monomer.

Claim 5

The process of claim 1 wherein the unsaturated carboxyl-containing monomer is methacrylic acid.

Claim 6

The process of claim 1 wherein the unsaturated carboxyl-containing monomer is acrylic acid.

Claim 7

The process of claim 1 wherein the unsaturated carboxyl-containing monomer is maleic anhydride, maleic acid, a half-ester of maleic acid, or mixture thereof.

Claim 8

A process for making a photoresist which comprises: preparing a photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of and being solely one or more non-gaseous compounds, containing at least two terminal ethylenic groups, having a boiling point above 100° C. and being selected from the group consisting of an unsaturated ester of a polyol, an unsaturated amide, and a vinyl ester; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerization inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: a first monomeric material which contains one or more non-acidic vinyl compounds selected from the group having the general formula: ##EQU2## wherein, when X is hydrogen, Y is OOCR 1 , OR 1 , OCR 1 , COOR 1 , CN, CH=CH 2 , ##EQU3## or Cl; when X is methyl, Y is COOR 1 , CN, CH=CH 2 , or ##EQU4## and when X is chlorine, Y is Cl; and wherein R 1 is an alkyl group having from 1 to 12 carbon atoms, a phenyl group or a benzyl group and R 3 and R 4 are hydrogen, an alkyl group having from 1 to 12 carbon atoms or a benzyl group; and a second monomeric material which consists essentially of one or more alpha,beta-unsaturated carboxyl-containing monomers having from 3 to 15 carbon atoms; wherein the ratio of the first monomeric material to the second monomeric material is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base; exposing a portion of said photopolymerizable layer to actinic light; and washing said layer with a dilute aqueous alkaline solution to dissolve the unexposed portion of the photopolymerizable layer.

Claim 9

A process for making a photoresist which comprises: preparing a photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of and being solely one or more non-gaseous compounds, containing at least two terminal ethylenic groups, having a boiling point above 100° C. and being selected from the group consisting of an unsaturated ester of a polyol, an unsaturated amide, and a vinyl ester; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerization inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: a first monomeric material which contains one or more non-acidic vinyl compounds selected from the group having the general formula: ##EQU2## wherein, when X is hydrogen, Y is OOCR 1 , OR 1 , OCR 1 , COOR 1 , CN, CH=CH 2 , ##EQU3## or Cl; when X is methyl, Y is COOR 1 , CN, CH=CH 2 , or ##EQU4## and when X is chlorine, Y is Cl; and wherein R 1 is an alkyl group having from 1 to 12 carbon atoms, a phenyl group or a benzyl group and R 3 and R 4 are hydrogen, an alkyl group having from 1 to 12 carbon atoms or a benzyl group; and a second monomeric material which consists essentially of one or more alpha,beta-unsaturated carboxyl-containing monomers having from 3 to 15 carbon atoms; wherein the ratio of the first monomeric material to the second monomeric material is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base; exposing a portion of said photopolymerizable layer to actinic light; and washing said layer with a dilute aqueous alkaline solution to dissolve the unexposed portion of the photopolymerizable layer.

Claim 10

A process for making photoresist which comprises: preparing a photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of trimethylolpropane triacrylate and tetraethyleneglycol diacrylate; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerizable inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of sytrene and monobutyl maleate, wherein the ratio of the sytrene to the monobutyl maleate is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base; exposing a portion of said photopolymerizable layer to actinic light; and washing said layer with a dilute aqueous alkaline solution to dissolve the unexposed portion of the photopolymerizable layer.

Claim 11

A process for making photoresist which comprises: preparing a photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of trimethylolpropane triacrylate and tetraethyleneglycol diacrylate; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerizable inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of sytrene and monobutyl maleate, wherein the ratio of the sytrene to the monobutyl maleate is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base; exposing a portion of said photopolymerizable layer to actinic light; and washing said layer with a dilute aqueous alkaline solution to dissolve the unexposed portion of the photopolymerizable layer.

Claim 12

A process for making a photoresist which comprises: preparing a photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of pentaerythritol acrylates; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerizable inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of styrene and monobutyl maleate, wherein the ratio of the sytrene to the monobutyl maleate is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base; exposing a portion of said photopolymerizable layer to actinic light; and washing said layer with a dilute aqueous alkaline solution to dissolve the unexposed portion of the photopolymerizable layer.

Claim 13

A process for making a photoresist which comprises: preparing a photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of pentaerythritol acrylates; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerizable inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of styrene and monobutyl maleate, wherein the ratio of the sytrene to the monobutyl maleate is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base; exposing a portion of said photopolymerizable layer to actinic light; and washing said layer with a dilute aqueous alkaline solution to dissolve the unexposed portion of the photopolymerizable layer.

Claim 14

A process for making a photoresist which comprises: preparing a photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of pentaerythritol acrylates; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerizable inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of vinyl acetate and crotonic acid, wherein the ratio of the vinyl acetate to the crotonic acid is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base; exposing a portion of said photopolymerizable layer to actinic light; and washing said layer with a dilute aqueous alkaline solution to dissolve the unexposed portion of the photopolymerizable layer.

Claim 15

A process for making a photoresist which comprises: preparing a photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of pentaerythritol acrylates; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerizable inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of vinyl acetate and crotonic acid, wherein the ratio of the vinyl acetate to the crotonic acid is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base; exposing a portion of said photopolymerizable layer to actinic light; and washing said layer with a dilute aqueous alkaline solution to dissolve the unexposed portion of the photopolymerizable layer.

Claim 16

The process of claim 8 wherein the photoinitiated free-radical generating addition polymerizing initiating system is an admixture of benzophenone and 4,4'-bis-(dimethylamino)-benzophenone and the thermal-addition polymerizable inhibitor is 2,2'-methylene-bis(4-ethyl-6-tert-butyl phenol).

Claim 17

The process of claim 8 wherein the ratio of the styrene to monobutyl maleate in the binding agent is from about 35:65 to 70:30.

Claim 18

The process of claim 9 wherein the photoinitiated free-radical generating addition polymerizing initiating system is an admixture of benzophenone and 4,4'-bis(dimethylamino)-benzophenone and the thermal-addition polymerizable inhibitor is 2,2'-methylene-bis(4-ethyl-6-tert-butyl phenol).

Claim 19

The process of claim 9 wherein the ratio of the styrene to monobutyl maleate in the binding agent is from about 35:65 to 70:30.

Claim 20

The process of claim 10 wherein the vinyl acetate-crotonic acid ratio is from 70:30 to 95:5.

Claim 21

The process of claim 7 wherein the photopolymerizable layer is supported on a metallic substrate prior to said washing step.

Claim 22

A coated composition which comprises a metallic substrate of copper or a copper alloy coated with a photopolymerizable composition comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of and being solely one or more non-gaseous compounds, containing at least two terminal ethylenic groups, having a boiling point above 100° C. and being selected from the group consisting of an unsaturated ester of a polyol, an unsaturated amide, and a vinyl ester; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerization inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: a first monomeric material which contains one or more non-acidic vinyl compounds selected from the group having the general formula: ##SPC3## wherein R is hydrogen, an alkyl group having from 1 to 6 carbon atoms or a halo group; and a second monomeric material which consists essentially of one or more alpha,beta-unsaturated carboxyl-containing monomers having from 3 to 15 carbon atoms; wherein the ratio of the first monomeric material to the second monomeric material is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base.

Claim 23

A coated composition which comprises a metallic substrate of copper or a copper alloy coated with a photopolymerizable composition comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of and being solely one or more non-gaseous compounds, containing at least two terminal ethylenic groups, having a boiling point above 100° C. and being selected from the group consisting of an unsaturated ester of a polyol, an unsaturated amide, and a vinyl ester; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerization inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: a first monomeric material which contains one or more non-acidic vinyl compounds selected from the group having the general formula: ##SPC3## wherein R is hydrogen, an alkyl group having from 1 to 6 carbon atoms or a halo group; and a second monomeric material which consists essentially of one or more alpha,beta-unsaturated carboxyl-containing monomers having from 3 to 15 carbon atoms; wherein the ratio of the first monomeric material to the second monomeric material is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base.

Claim 24

The coated composition of claim 17 wherein the photopolymerizable composition is cast into a film onto the substrate from solution.

Claim 25

The coated composition of claim 17 wherein the photopolymerizable composition is laminated as a precast film onto the substrate.

Claim 26

The coated composition of claim 17 wherein a portion of the photopolymerizable composition is insolubilized by exposure to actinic light.

Claim 27

A coated composition which comprises a metallic substrate of copper or a copper alloy; alloy coated with a photopolymerizable composition comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of and being solely one or more non-gaseous compounds, containing at least two terminal ethylenic groups, having a boiling point above 100° C. and being selected from the group consisting of an unsaturated ester of a polyol, an unsaturated amide, and a vinyl ester; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerization inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: a first monomeric material which contains one or more non-acidic vinyl compounds selected from the group having the general formula: ##EQU5## wherein, when X is hydrogen, Y is OOCR 1 , OR 1 , OCR 1 , COOR 1 , CN, CH=CH 2 , ##EQU6## or Cl; when X is methyl, Y is COOR 1 , CN, CH=CH 2 , ##EQU7## and when X is chlorine, Y is Cl; and wherein R 1 is an alkyl group having from 1 to 12 carbon atoms, a phenyl group or a benzyl group and R 3 and R 4 are hydrogen, an alkyl group having from 1 to 12 carbon atoms or a benzyl group; and a second monomeric material which consists essentially of one or more alpha,beta-unsaturated carboxyl-containing monomers having from 3 to 15 carbon atoms; wherein the ratio of the first monomeric material to the second monomeric material is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base.

Claim 28

A coated composition which comprises a metallic substrate of copper or a copper alloy; alloy coated with a photopolymerizable composition comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of and being solely one or more non-gaseous compounds, containing at least two terminal ethylenic groups, having a boiling point above 100° C. and being selected from the group consisting of an unsaturated ester of a polyol, an unsaturated amide, and a vinyl ester; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerization inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: a first monomeric material which contains one or more non-acidic vinyl compounds selected from the group having the general formula: ##EQU5## wherein, when X is hydrogen, Y is OOCR 1 , OR 1 , OCR 1 , COOR 1 , CN, CH=CH 2 , ##EQU6## or Cl; when X is methyl, Y is COOR 1 , CN, CH=CH 2 , ##EQU7## and when X is chlorine, Y is Cl; and wherein R 1 is an alkyl group having from 1 to 12 carbon atoms, a phenyl group or a benzyl group and R 3 and R 4 are hydrogen, an alkyl group having from 1 to 12 carbon atoms or a benzyl group; and a second monomeric material which consists essentially of one or more alpha,beta-unsaturated carboxyl-containing monomers having from 3 to 15 carbon atoms; wherein the ratio of the first monomeric material to the second monomeric material is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base.

Claim 29

The coated composition of claim 21 wherein the photopolymerizable composition is cast into a film onto the substrate from solution.

Claim 30

The coated composition of claim 21 wherein the photopolymerizable composition is laminated as a precast film onto the substrate.

Claim 31

The coated composition of claim 21 wherein a portion of the photopolymerizable composition is insolubilized by exposure to actinic light.

Claim 32

A laminate which comprises: (1) a metallic substrate of copper or a copper alloy, (2) an intermediate photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of and being solely one or more non-gaseous compounds, containing at least two terminal ethylenic groups, having a boiling point above 100° C. and being selected from the group consisting of an unsaturated ester of a polyol, an unsaturated amide, and a vinyl ester; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerization inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: a first monomeric material which contains one or more non-acidic vinyl compounds selected from the group having the general formula: ##SPC4## wherein R is hydrogen, an alkyl group having from 1 to 6 carbon atoms or a halo group; and a second monomeric material which consists essentially of one or more alpha,beta-unsaturated carboxyl-containing monomers having from 3 to 5 carbon atoms; wherein the ratio of the first monomeric material to the second monomeric material is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base, and (3) a cover layer which is impervious to oxygen.

Claim 33

A laminate which comprises: (1) a metallic substrate of copper or a copper alloy, (2) an intermediate photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of and being solely one or more non-gaseous compounds, containing at least two terminal ethylenic groups, having a boiling point above 100° C. and being selected from the group consisting of an unsaturated ester of a polyol, an unsaturated amide, and a vinyl ester; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerization inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: a first monomeric material which contains one or more non-acidic vinyl compounds selected from the group having the general formula: ##SPC4## wherein R is hydrogen, an alkyl group having from 1 to 6 carbon atoms or a halo group; and a second monomeric material which consists essentially of one or more alpha,beta-unsaturated carboxyl-containing monomers having from 3 to 5 carbon atoms; wherein the ratio of the first monomeric material to the second monomeric material is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base, and (3) a cover layer which is impervious to oxygen.

Claim 34

The laminate of claim 25 wherein the copolymer is of sytrene and an unsaturated carboxyl-containing monomer.

Claim 35

The laminate of claim 25 wherein the unsaturated carboxyl-containing monomer is methacrylic acid.

Claim 36

The laminate of claim 25 wherein the unsaturated carboxyl-containing monomer is acrylic acid.

Claim 37

The laminate of claim 25 wherein the unsaturated carboxyl-containing monomer is maleic anhydride, maleic acid, a half-ester of maleic acid, or mixture thereof.

Claim 38

A laminate which comprises: (1) a metallic substrate of copper or a copper alloy, (2) an intermediate photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of and being solely one or more non-gaseous compounds, containing at least two terminal ethylenic groups, having a boiling point above 100° C. and being selected from the group consisting of an unsaturated ester of a polyol, an unsaturated amide, and a vinyl ester; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerization inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: a first monomeric material which contains one or more non-acidic vinyl compounds selected from the group having the general formula: ##EQU8## wherein, when X is hydrogen, Y is OOCR 1 , OR 1 , OCR 1 , COOR 1 , CN, CH=CH 2 , ##EQU9## or Cl; when X is methyl, Y is COOR 1 , CN, CH=CH 2 , or ##EQU10## and when X is chlorine, Y is Cl; and wherein R 1 is an alkyl group having from 1 to 12 carbon atoms, a phenyl group or a benzyl group and R 3 and R 4 are hydrogen, an alkyl group having from 1 to 12 carbon atoms or a benzyl group; and a second monomeric material which consists essentially of one or more alpha,beta-unsaturated carboxyl-containing monomers having from 3 to 15 carbon atoms; wherein the ratio of the first monomeric material to the second monomeric material is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base, and (3) a cover layer which is impervious to oxygen.

Claim 39

A laminate which comprises: (1) a metallic substrate of copper or a copper alloy, (2) an intermediate photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of and being solely one or more non-gaseous compounds, containing at least two terminal ethylenic groups, having a boiling point above 100° C. and being selected from the group consisting of an unsaturated ester of a polyol, an unsaturated amide, and a vinyl ester; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerization inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: a first monomeric material which contains one or more non-acidic vinyl compounds selected from the group having the general formula: ##EQU8## wherein, when X is hydrogen, Y is OOCR 1 , OR 1 , OCR 1 , COOR 1 , CN, CH=CH 2 , ##EQU9## or Cl; when X is methyl, Y is COOR 1 , CN, CH=CH 2 , or ##EQU10## and when X is chlorine, Y is Cl; and wherein R 1 is an alkyl group having from 1 to 12 carbon atoms, a phenyl group or a benzyl group and R 3 and R 4 are hydrogen, an alkyl group having from 1 to 12 carbon atoms or a benzyl group; and a second monomeric material which consists essentially of one or more alpha,beta-unsaturated carboxyl-containing monomers having from 3 to 15 carbon atoms; wherein the ratio of the first monomeric material to the second monomeric material is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base, and (3) a cover layer which is impervious to oxygen.

Claim 40

A laminate which comprises: (1) a metallic substrate of copper or a copper alloy, (2) an intermediate photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of trimethylolpropane triacrylate and tetraethyleneglycol diacrylate; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerizable inihibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of styrene and monobutyl maleate, wherein the ratio of the styrene to the monobutyl maleate is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base, and (3) a cover layer which is impervious to oxygen.

Claim 41

A laminate which comprises: (1) a metallic substrate of copper or a copper alloy, (2) an intermediate photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of trimethylolpropane triacrylate and tetraethyleneglycol diacrylate; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initating system; C. from 0.001 to 5 parts by weight of a thermaladdition polymerizable inihibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of styrene and monobutyl maleate, wherein the ratio of the styrene to the monobutyl maleate is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base, and (3) a cover layer which is impervious to oxygen.

Claim 42

The laminate of claim 31 wherein the photoinitiated free-radical generating addition polymerizing initiating system is an admixture of benzophenone and 4,4'-bis-(dimethylamino)-benzophenone and the thermal-addition polymerizable inhibitor is 2,2'-methylene-bis(4-ethyl-6-tert-butyl phenol).

Claim 43

The laminate of claim 31 wherein the ratio of the styrene to monobutyl maleate in the binding agent is from about 35:65 to 70:30.

Claim 44

A laminate which comprises: (1) a metallic substrate of copper or a copper alloy, (2) an intermediate photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of pentaerythritol acrylates; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polmerizable inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of styrene and monobutyl maleate, wherein the ratio of the styrene to the monobutyl maleate is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base, and (3) a cover layer which is impervious to oxygen.

Claim 45

A laminate which comprises: (1) a metallic substrate of copper or a copper alloy, (2) an intermediate photopolymerizable layer comprising: A. from 10 to 60 parts by weight of an addition polymerizable material consisting essentially of pentaerythritol acrylates; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermaladdition polmerizable inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of styrene and monobutyl maleate, wherein the ratio of the styrene to the monobutyl maleate is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base, and (3) a cover layer which is impervious to oxygen.

Claim 46

The laminate of claim 34 wherein the photoinitiated free-radical generating addition polymerizing initiating system is an admixture of benzophenone and 4,4'-bis(dimethylamino)-benzophenone and the thermal-addition polymerizable inhibitor is 2,2'-methylene-bis(4-ethyl-6-tert-butyl phenol).

Claim 47

The laminate of claim 34 wherein the ratio of the styrene to monobutyl maleate in the binding agent is from about 35:65 to 70:30.

Claim 48

A laminate which comprises: (1) a metallic substrate of copper or a copper alloy, (2) an intermediate photopolymerizable layer comprising: A. from 10 to 60 parts by weight an addition polymerizable material consisting essentially of pentaerythritol acrylates; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermal-addition polymerizable inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of vinyl acetate and crotonic acid, wherein the ratio of the vinyl acetate to the crotonic acid is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base, and (3) a cover layer which is impervious to oxygen.

Claim 49

A laminate which comprises: (1) a metallic substrate of copper or a copper alloy, (2) an intermediate photopolymerizable layer comprising: A. from 10 to 60 parts by weight an addition polymerizable material consisting essentially of pentaerythritol acrylates; B. from 0.001 to 10 parts by weight of a photoinitiated free-radical generating addition polymerizing initiating system; C. from 0.001 to 5 parts by weight of a thermal-addition polymerizable inhibitor; and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of vinyl acetate and crotonic acid, wherein the ratio of the vinyl acetate to the crotonic acid is sufficient to render the binding agent soluble in a dilute aqueous solution containing from 0.01 to 10% of a water-soluble base, and (3) a cover layer which is impervious to oxygen.

Claim 50

The laminate of claim 37 wherein the vinyl acetate-crotonic acid ratio is from 70:30 to 95:5.