EP0128014A2
Expired / Lapsed
EP
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Photopolymerizable composition, products made therefrom and processes for preparing such products
Assignee: Morton International LLC
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Filing: 1984-05-31
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Granted: —
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Expires: 2004-05-31
Abstract
Abstract A photopolymerizable composition comprised of an addition polymerizable material, a photoinitiator, a thermal addition polymerization inhibitor and a polymeric binding agent. The addition polymerizable material is comprised of a defined monoethylenically unsaturated acrylate and one or more non-gaseous compounds having at least two terminal ethylenic groups. The photopolymerizable composition displays superior flexibility and develops and strips more efficiently when compared to a like composition but in the absence of the acrylate. The photopolymerizable composition may be in the form of sheet or roll on a film support which can be laminated to a substrate and can be used in the preparation of printed circuit boards.
Inventors
- 👤 Melvin A. Lipson
- 👤 Gene A. Derrico
- 👤 Sung Yong Tark
- 👤 Toshio Yamazaki
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-05 17:45
CPC Classifications
G; G03; G03F; G03F7/00; G03F7/004; G03F7/027; G03F7/028; G03F7/032; G03F7/033; Y; Y10; Y10S; Y10S430/00; Y10S430/1053; Y10S430/1055; Y10S430/106; Y10S430/111; Y10S430/114; Y10S430/118
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
375 words
A photopolymerizable composition comprising: A. from 10 to 60-parts by weight of an addition polymerizable material comprised of i) from 5 to 50 parts by weight of an , acrylate of the formula wherein m is from 1 to 4, n is from 1 to 12, R 1 is selected from H, CH 3 and mixtures thereof and R 2 is selected from unsubstituted phenyl, substituted phenyl, unsubstituted naphthenyl, substituted naphthenyl, branched or unbranched, substituted or unsubstituted alkyl having 1 to 12 carbon atoms, substituted or unsubstituted cycloalkyl having 5 or 6 carbon atoms in the ring and mixtures thereof and ii) from 5 to 50 parts by weight of one or more non gaseous compounds containing at least two terminal ethylenic groups and having a boiling point above 100°C B, from 0.001 to 20 parts by weight of a photo initiated free radical generating addition. polymerization initiating system; C from 0.001 to 5 parts by weight of a thermal addition polymerization inhibitory and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: i) a first monomeric material which contains one or more non acidic compounds having the general formulas wherein R is hydrogen. an alkyl group having from 1 to'6 carbon atoms or a halo group and wherein, when X is hydrogen. Y is OOCR 1 , OR 1 , OCR 1 , COOR 1 , CN- CH = C H 2 or Cl when Xis methyl, Y is COOR 1 , CN- CH=CH 2 . or 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 R3 and R4 are hydrogen, an alkyl group having from 1 to 12 carbon atoms or a benzyl group: and II. a second monomeric material which consists essentially of one or more alpha. beta ethylenically unsaturated carboxylic acid-or anhydride-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 substantially all of the binding agent soluble in a substant-- ially wholly aqueous solution containing 2% by weight of sodium carbonate.
Claim 2
Dependent Claim
375 words
A photopolymerizable composition comprising: A. from 10 to 60-parts by weight of an addition polymerizable material comprised of i) from 5 to 50 parts by weight of an , acrylate of the formula wherein m is from 1 to 4, n is from 1 to 12, R 1 is selected from H, CH 3 and mixtures thereof and R 2 is selected from unsubstituted phenyl, substituted phenyl, unsubstituted naphthenyl, substituted naphthenyl, branched or unbranched, substituted or unsubstituted alkyl having 1 to 12 carbon atoms, substituted or unsubstituted cycloalkyl having 5 or 6 carbon atoms in the ring and mixtures thereof and ii) from 5 to 50 parts by weight of one or more non gaseous compounds containing at least two terminal ethylenic groups and having a boiling point above 100°C B, from 0.001 to 20 parts by weight of a photo initiated free radical generating addition. polymerization initiating system; C from 0.001 to 5 parts by weight of a thermal addition polymerization inhibitory and D. from 40 to 90 parts by weight of a preformed macromolecular polymeric binding agent which is a polymer of: i) a first monomeric material which contains one or more non acidic compounds having the general formulas wherein R is hydrogen. an alkyl group having from 1 to'6 carbon atoms or a halo group and wherein, when X is hydrogen. Y is OOCR 1 , OR 1 , OCR 1 , COOR 1 , CN- CH = C H 2 or Cl when Xis methyl, Y is COOR 1 , CN- CH=CH 2 . or 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 R3 and R4 are hydrogen, an alkyl group having from 1 to 12 carbon atoms or a benzyl group: and II. a second monomeric material which consists essentially of one or more alpha. beta ethylenically unsaturated carboxylic acid-or anhydride-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 substantially all of the binding agent soluble in a substant-- ially wholly aqueous solution containing 2% by weight of sodium carbonate.
Claim 3
Dependent Claim
21 words
The photopolymerizable composition of claim 1 wherein n is from 2 to 8 and R 2 is substituted or unsubstituted phenyl.
Claim 4
Dependent Claim
27 words
The photopolymerizable composition of claim 2 wherein m is 2 or 3, n is 2 or 3. R 1 is H and R 2 is unsubstituted phenyl.
Claim 5
Dependent Claim
44 words
The photopolymerizable composition as claimed in any preceding claim, wherein the non-gaseous compounds containing at least two terminal ethylenic groups and having a boiling point above 100°C are selected from unsaturated ester of a polyol, an unsaturated amide, a vinyl ester and mixtures thereof.
Claim 6
Dependent Claim
22 words
The photopolymerizable composition of claim 4 wherein the non-gaseous compounds are selected from trimethylolpropane triacrylate. tetraethyleneglycol diacrylate, tripropyleneglycol diacrylate and mixtures thereof.
Claim 7
Dependent Claim
13 words
The photopolymerizable composition of claim 4 wherein the non-gaseous compounds comprise tripropyleneglycol diacrylate.
Claim 8
Dependent Claim
13 words
The photopolymerizable composition of claim 4 wherein the non-gaseous compounds comprise pentaerythritol acrylates.
Claim 9
Dependent Claim
22 words
The photopolymerizable composition as claimed in any preceding claim wherein the binding agent has the first monomeric material having the general formula
Claim 12
Dependent Claim
25 words
The photopolymerizable composition of claim 8 wherein the binding agent is a copolymer of styrene and monobutyl maleate in a ratio offrom 35:65 to 70:30.
Claim 13
Dependent Claim
35 words
lO. The photopolymerizable composition as claimed in any one of claims 1 to 7 wherein the binding agent is a copolymer of vinyl acetate and crotonic acid in a ratio of from 70:30 to 95:5.
Claim 14
Dependent Claim
53 words
The photopolymerizable composition as claimed in any one of claims 1 to 7 wherein the binding agent is a mixture of a copolymer of styrene and monobutyl maleate in a ratio of from 35:65 to 70:30 with a copolymer of vinyl acetate and crotonic acid in a ratio of from 70:30 to 95:5.
Claim 15
Dependent Claim
43 words
The photopolymerizable composition as claimed in any one of claims 1 to 7 wherein the binding agent is a copolymer of an acrylate-type monomer and one or more alpha, beta-ethylenically unsaturated carboxylic acid- or anhydride-containing monomers having from 3 to 15 carbon atoms.
Claim 16
Dependent Claim
46 words
The photopolymerizable composition as claimed in any one of claims 1 to 7 wherein the binding agent is a copolymer of i) ii) an acrylate-type monomer and iii) one or more alpha, beta-ethylenically unsaturated carboxylic acid- or anhydride-containing monomers having from 3 to 15 carbon atoms.
Claim 17
Dependent Claim
47 words
The photopolymerizable composition of claim 13 wherein the acrylate type monomer is selected from alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate and mixtures thereof wherein the alkyl groups have from 1 to 12 carbon atoms and the hydroxyalkyl groups have from 2 to 12 carbon atoms.
Claim 18
Dependent Claim
24 words
A sheet or roll of a photopolymerizable composition on a flexible film support, wherein said photopolymerizable composition is as defined in any preceding claim.
Claim 19
Dependent Claim
26 words
The sheet or roll of claim l5 wherein the acrylate is selected from substituted and unsubstituted phenoxypolyethoxyethyl acrylates, substituted and unsubstituted phenoxypolypropoxypropyl acrylates and mixtures thereof.
Claim 20
Dependent Claim
15 words
The sheet or roll of claim 16 wherein the acrylate is an unsubstituted phenoxypolyethoxyethyl acrylate.
Claim 21
Dependent Claim
25 words
A coated composition of a photopolymerizable composition on a substrate, wherein said photopolymerizable composition comprising as defined in any one of claims 1 to 14.
Claim 22
Dependent Claim
14 words
The coated composition of claim 18 wherein the substrate is comprised of a metal.
Claim 23
Dependent Claim
18 words
The coated composition of claim 19 wherein the metal is selected from steel, aluminium, copper, zinc and magnesium.
Claim 24
Dependent Claim
13 words
The coated composition of claim 18 wherein the substrate is comprised of plastics.
Claim 25
Dependent Claim
14 words
The coated composition of claim 18 wherein the substrate is a copper clad laminate.
Claim 26
Dependent Claim
15 words
The coated composition of claim 22 wherein the substrate is a copper clad, epoxy-fiberglass laminate.
Claim 27
Dependent Claim
144 words
A process for preparing a printed circuit board comprising: A. laminating on-to a printed circuit board precursor a photopolymerizable composition as claimed in any one of claims 1 to 14; B. exposing selected portions of the photopolymerizable composition to actinic radiation sufficient to obtain photopolymerization of said exposed portions; C. removing the unexposed portions of the composition to bare portions of the circuit board precursor by contact with a substantially wholly aqueous solution having an alkalinity at least as great as a 2% by weight solution of sodium carbonate; D. modifying the bared portions of the circuit board precursor to form a selective electrically conductive pattern; and E. stripping the exposed selected portions of the composition from the circuit board by contact with a substantially wholly aqueous solution having an alkalinity at least as great as a 3% by weight solution of sodium hydroxide.
Claim 28
Dependent Claim
18 words
The process of claim 24 wherein the printed circuit board precursor is a copper clad, epoxy fiberglass laminate.
Claim 29
Dependent Claim
17 words
The process of claim 24 wherein the printed circuit board precursor is a flexible, copper clad laminate.
Claim 30
Dependent Claim
40 words
The process as claimed in any one of claims 24 to 26 wherein the printed circuit board precursor has a metallic material on both sides and the photopolymerizable composition is laminated to both sides on top of said metallic material.
Claim 31
Dependent Claim
40 words
The process as claimed in any one of claims 24 to 27 wherein the photopolymerizable composition is laminated to the printed circuit board precursor in the form of a sheet or a portion of a roll on a film support.
Claim 32
Dependent Claim
22 words
The process as claimed in claims 24 to 28 wherein the bared portions of the circuit board precursor are modified by etching.
Claim 33
Dependent Claim
25 words
The process as claimed in any one of claims 24 to 28 wherein the bared portions of the circuit board precursor are modified by plating.
Claim 34
Dependent Claim
48 words
The process as claimed in any one of claims 24 to 30 wherein the time required for stripping the exposed selected portions of the composition is reduced by 10 to 80% compared to a like composition absent said acrylate in the addition polymerizable material under the same conditions.
Claim 35
Dependent Claim
144 words
A process for chemical machining comprising: A. laminating onto both sides of a metallic sheet or foil a polymerizable composition as claimed in any one of claims 1 to 14; B. exposing selected portions of the photopolymerizable composition to actinic radiation sufficient to obtain photopolymerization of said exposed portions; C. removing the unexposed portions of the composition to bare portions of the sheet or foil by contact with a substantially wholly aqueous solution having an alkalinity at least as great as a 2% by weight solution of sodium carbonate; D. etching the bared portions of the sheet or foil to form the desired pattern; and E. stripping the exposed selected portions of the composition from the etched sheet or foil by contact with a substantially wholly aqueous solution having an alkalinity at least as great as a 3% by weight solution of soidum hydroxide.
References Cited (Backward Citations)
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