US5232815A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Autodeposition emulsion and methods of using thereof to selectively protect metallic surfaces
Assignee: MacDermid Acumen Inc
•
Filing: 1992-04-20
•
Granted: 1993-08-03
•
Expires: 2012-04-20
Abstract
Abstract A coating of resin and photoactive functionality is autodeposited from an emulsion onto a metallic substrate in order to selectively protect the substrate from corrosive environments such as etchant processes. An acid and oxidizing agent are included in the emulsion so that when the substrate is immersed in the emulsion the resin and photoactive functionality autodeposits. The resulting coating can be exposed to actinic radiation in an image-wise fashion and developed in an alkaline solution to develop the image created. In instances where the emulsion and process are used to make circuit boards, the metallic surface uncovered during developing is then etched away, leaving only the coated sections of the surface. The resulting coated surfaces will be the circuit traces of the circuit board.
Inventors
- 👤 Alan R. Browne
- 👤 Daniel J. Hart
- 👤 Alan F. Becknell
- 👤 Betsy Elzufon
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 03:21
CPC Classifications
H; H05; H05K; H05K3/00; H05K3/02; H05K3/06; H05K3/061; H05K3/064; B; B05; B05D; B05D7/00; B05D7/14; B05D7/142; G; G03; G03F; G03F7/00; G03F7/16; B05D3/00; B05D3/06; B05D3/061; B05D3/065; B05D3/067; B05D7/144; H05K2203/00; H05K2203/07; H05K2203/0756; H05K2203/0759; H05K2203/0779; H05K2203/0786; H05K2203/0796
Claims Analysis
Total Claims: 49
Claim 1
Independent Claim
137 words
Method of selectively coating a metallic surface, the method comprising (a) immersing said metallic surface in an autodepositable, acidic, aqueous photoresist emulsion having a pH of about 1 to 5 and having the capability of being developed by an aqueous base solution, said emulsion comprising (i) a water-insoluble acid-containing resin; (ii) a photoactive functionality; (iii) an acid; (iv) an oxidizing agent; and (v) a surfactant, wherein (i)-(v) are present in amounts and the surface is immersed for a period of time sufficient to autodeposit a coating of resin (i) and photoactive functionality (ii) on said metallic surface; (b) exposing said coating of resin (i) and photoactive functionality (ii) to actinic radiation in an image-wise fashion; and (c) immersing said exposed coated surface from (b) above in an aqueous base solution to develop an image on said surface.
Claim 2
Dependent Claim
137 words
Method of selectively coating a metallic surface, the method comprising (a) immersing said metallic surface in an autodepositable, acidic, aqueous photoresist emulsion having a pH of about 1 to 5 and having the capability of being developed by an aqueous base solution, said emulsion comprising (i) a water-insoluble acid-containing resin; (ii) a photoactive functionality; (iii) an acid; (iv) an oxidizing agent; and (v) a surfactant, wherein (i)-(v) are present in amounts and the surface is immersed for a period of time sufficient to autodeposit a coating of resin (i) and photoactive functionality (ii) on said metallic surface; (b) exposing said coating of resin (i) and photoactive functionality (ii) to actinic radiation in an image-wise fashion; and (c) immersing said exposed coated surface from (b) above in an aqueous base solution to develop an image on said surface.
Claim 3
Dependent Claim
12 words
A method according to claim 1 wherein said metallic surface is copper.
Claim 4
Dependent Claim
27 words
A method according to claim 2 wherein said copper surface is a layer in a laminate comprising at least one copper layer laminated onto a reinforcing layer.
Claim 5
Dependent Claim
15 words
A method according to claim 1 wherein photoactive functionality (ii) is a positive acting functionality.
Claim 6
Dependent Claim
36 words
A method according to claim 4 wherein the positive acting functionality is a member of the group consisting of polyoxymethylene, o-nitrocarbinol esters, o-nitrophenyl acetals and corresponding esters, benzoquinone diazide sulphonic esters, and naphthoquinone diazide sulphonic esters.
Claim 7
Dependent Claim
34 words
A method according to claim 4 wherein the positive acting functionality is o-nitrocarbinol ester and wherein the resin is an emulsion polymerization copolymer product of said nitrocarbinol ester with methyl methacrylate and acrylic acid.
Claim 8
Dependent Claim
31 words
A method according to claim 4 wherein the positive acting functionality is o-nitrocarbinol ester and wherein the resin is an emulsion polymerization copolymer product of said nitrocarbinol ester with vinylidene chloride.
Claim 9
Dependent Claim
38 words
A method according to claim 4 wherein the positive acting functionality is a 2-diazo-1-naphthoquinone sulfonate triester of 2,3,4-trihydroxy benzophenone and the resin is a novolak and wherein the functionality and resin are emulsified together as chemically separate components.
Claim 10
Dependent Claim
19 words
A method according to claim 4 wherein the positive acting functionality is 2-diazo-1-naphthoquinone sulfonate ester of a novolak resin.
Claim 11
Dependent Claim
19 words
A method according to claim 1 wherein the photoactive functionality (ii is a negative acting functionality and a photoinitiator.
Claim 12
Dependent Claim
13 words
A method according to claim 10 wherein the negative acting functionality comprises acrylate.
Claim 13
Dependent Claim
39 words
A method according to claim 10 wherein the negative acting functionality is an acrylate and the resin is a styrene/butadiene/methacrylic acid copolymer wherein the resin is in the form of a latex and the negative functionality is added thereto.
Claim 14
Dependent Claim
58 words
A method according to claim 11 wherein the acrylate is a member of the group consisting of ethyleneglycol diacrylate, ethyleneglycol dimethacrylate, propyleneglycol diacrylate, propyleneglycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, trimethylolpropane ethoxylate trimethacrylate, trimethylolpropane propoxylate trimethacrylate, bisphenol A diacrylate, phenoxyethyl methacrylate, hexanediol diacrylate, neopentylglycol diacrylate, neopentyl propoxylate diacrylate, pentaerythritol triacrylate, dipentaerythritol hydroxypentaacrylate, and polyethyleneglycol diacrylate.
Claim 15
Dependent Claim
38 words
A method according to claim 10 wherein the negative acting functionality is ethoxylated trimethylolpropane triacrylate and the resin is esterified styrene/maleic anhydride copolymer and wherein the negative acting functionality and resin are emulsified together as chemically separate components.
Claim 16
Dependent Claim
43 words
A method according to claim 10 wherein the negative acting functionality is a mixture of dipentaerythritol hydroxypentacrylate and triethylene glycol dimethacrylate and the said resin is styrene/acrylic acid copolymer wherein the negative acting functionality and resin are emulsified together as chemically separate components.
Claim 17
Dependent Claim
49 words
A method according to claim 1 wherein the resin is a member of the group consisting of butadiene/acrylonitrile/methacrylic acid styrene/acrylic acid novolak styrene/butadiene/acrylic acid styrene/butadiene/methacrylic acid styrene/butadiene/itaconic acid styrene/butadiene/maleic acid styrene/butadiene/butylacrylate/acrylic acid styrene/butadiene/butylacrylate/methacrylic acid styrene/butadiene/butylacrylate/itaconic acid styrene/butadiene/butylacrylate/maleic acid styrene/ethyl acrylate/methacrylic acid styrene/maleic anhydride styrene/methacrylic acid and vinylidene chloride/methacrylic acid.
Claim 18
Dependent Claim
25 words
A method according to claim 1 wherein the acid is a member of the group consisting of hydrochloric, hydrofluoric, phosphoric, citric, sulfuric and acetic acids.
Claim 19
Dependent Claim
25 words
A method according to claim 5 wherein the acid is a member of the group consisting of hydrochloric, hydrofluoric, phosphoric, citric, sulfuric and acetic acids.
Claim 20
Dependent Claim
25 words
A method according to claim 13 wherein the acid is a member of the group consisting of hydrochloric, hydrofluoric, phosphoric, citric, sulfuric and acetic acids.
Claim 21
Dependent Claim
13 words
A method according to claim 1 wherein the oxidizing agent is hydrogen peroxide.
Claim 22
Dependent Claim
13 words
A method according to claim 5 wherein the oxidizing agent is hydrogen peroxide.
Claim 23
Dependent Claim
13 words
A method according to claim 13 wherein the oxidizing agent is hydrogen peroxide.
Claim 24
Dependent Claim
19 words
A method according to claim 1 wherein said developer in step (c) is aqueous sodium hydroxide or sodium carbonate.
Claim 25
Independent Claim
171 words
A method of making electrical circuit traces from a metallic surface, the method comprising (a) immersing said metallic surface in an autodepositable, acidic, aqueous photoresist emulsion having a pH of about 1 to 5 and the capability of being developed by an aqueous base solution, said method comprising (i) a water-insoluble acid-containing resin; (ii) a photoactive functionality; (iii) an acid; (iv) an oxidizing agent; and (v) a surfactant, wherein (i)-(v) are present in amounts and the surface is immersed for a period of time sufficient to autodeposit a coating of resin (i) and photoactive functionality (ii) on said metallic surface; (b) exposing said coating of resin (i) and photoactive functionality (ii) to actinic radiation in an image-wise fashion; (c) immersing said exposed coated metallic surface from (b) above in an aqueous base solution to develop an image on said metallic surface; (d) immersing the developed surface from (c) in an etchant bath to remove metallic surfaces which were uncovered during step (c); and (e) stripping any remaining coating in a solvent.
Claim 26
Independent Claim
171 words
A method of making electrical circuit traces from a metallic surface, the method comprising (a) immersing said metallic surface in an autodepositable, acidic, aqueous photoresist emulsion having a pH of about 1 to 5 and the capability of being developed by an aqueous base solution, said method comprising (i) a water-insoluble acid-containing resin; (ii) a photoactive functionality; (iii) an acid; (iv) an oxidizing agent; and (v) a surfactant, wherein (i)-(v) are present in amounts and the surface is immersed for a period of time sufficient to autodeposit a coating of resin (i) and photoactive functionality (ii) on said metallic surface; (b) exposing said coating of resin (i) and photoactive functionality (ii) to actinic radiation in an image-wise fashion; (c) immersing said exposed coated metallic surface from (b) above in an aqueous base solution to develop an image on said metallic surface; (d) immersing the developed surface from (c) in an etchant bath to remove metallic surfaces which were uncovered during step (c); and (e) stripping any remaining coating in a solvent.
Claim 27
Dependent Claim
12 words
A method according to claim 24 wherein the metallic surface is copper.
Claim 28
Dependent Claim
28 words
A method according to claim 25 wherein said copper surface is a layer in a laminate comprising at least one layer of copper laminated onto a reinforcing layer.
Claim 29
Dependent Claim
13 words
A method according to claim 26 wherein said laminate has plated through holes.
Claim 30
Dependent Claim
16 words
A method according to claim 24 wherein the photoactive functionality (ii) is a positive acting functionality.
Claim 31
Dependent Claim
36 words
A method according to claim 28 wherein the positive acting functionality is a member of the group consisting of polyoxymethylene, o-nitrocarbinol esters, o-nitrophenyl acetals and corresponding esters, benzoquinone diazide sulphonic esters, and naphthoquinone diazide sulphonic esters.
Claim 32
Dependent Claim
33 words
A method according to claim 28 wherein the positive acting functionality is o-nitrocarbinol ester and wherein the resin is an emulsion polymerization copolymer product of said ester with methyl methacrylate and acrylic acid.
Claim 33
Dependent Claim
30 words
A method according to claim 28 wherein the positive acting functionality is o-nitrocarbinol ester and wherein the resin is an emulsion polymerization copolymer product of said ester with vinylidene chloride.
Claim 34
Dependent Claim
40 words
A method according to claim 28 wherein the positive acting functionality is a 2-diazo-1-naphthoquinone sulfonate triester of 2,3,4-trihydroxy benzophenone and the resin is a novolak and wherein the positive acting functionality and resin are emulsified together as chemically separate components.
Claim 35
Dependent Claim
18 words
A method according to claim 28 wherein the positive acting functionality is 2-diazo-1-naphthoquinone sulfonate ester of novolak resin.
Claim 36
Dependent Claim
19 words
A method according to claim 24 wherein the photoactive functionality (ii) is a negative acting functionality and a photoinitiator.
Claim 37
Dependent Claim
13 words
A method according to claim 34 wherein the negative acting functionality comprises acrylate.
Claim 38
Dependent Claim
41 words
A method according to claim 34 wherein the negative acting functionality is an acrylate and the resin is a styrene/butadiene/methacrylic acid copolymer and wherein the resin is in the form of a latex and the negative acting functionality is added thereto.
Claim 39
Dependent Claim
58 words
A method according to claim 35 wherein the acrylate is a member of the group consisting of ethyleneglycol diacrylate, ethyleneglycol dimethacrylate, propyleneglycol diacrylate, propyleneglycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, trimethylolpropane propoxylate triacrylate, trimethylolpropane ethoxylate trimethacrylate, trimethylolpropane propoxylate trimethacrylate, bisphenol A diacrylate, phenoxyethyl methacrylate, hexanediol diacrylate, neopentylglycol diacrylate, neopentyl propoxylate diacrylate, pentaerythritol triacrylate, dipentaerythritol hydroxypentaacrylate and polyethyleneglycol diacrylate.
Claim 40
Dependent Claim
38 words
A method according to claim 34 wherein the negative acting functionality is ethoxylated trimethylolpropane triacrylate and the resin is esterified styrene/maleic anhydride copolymer and wherein the negative acting functionality and resin are emulsified together as chemically separate components.
Claim 41
Dependent Claim
43 words
A method according to claim 34 wherein the negative acting functionality is a mixture of dipentaerythritol hydroxypentacrylate and triethylene glycol dimethacrylate and the said resin is styrene/acrylic acid copolymer wherein the negative acting functionality and resin are emulsified together as chemically separate components.
Claim 42
Dependent Claim
47 words
A method according to claim 24 wherein the resin is a member of the group consisting of butadiene/acrylonitrile/methacrylic acid styrene/acrylic acid novolak styrene/butadiene/acrylic acid styrene/butadiene/itaconic acid styrene/butadiene/maleic acid styrene/butadiene/butylacrylate/acrylic acid styrene/butadiene/butylacrylate/methacrylic acid styrene/butadiene/butylacrylate/itaconic acid styrene/butadiene/butylacrylate/maleic acid styrene/ethyl acrylate/methacrylic acid styrene/maleic anhydride styrene/methacrylic acid and vinylidene chloride/methacrylic acid.
Claim 43
Dependent Claim
25 words
A method according to claim 24 wherein the acid is a member of the group consisting of hydrochloric, hydrofluoric, phosphoric, citric, sulfuric and acetic acids.
Claim 44
Dependent Claim
25 words
A method according to claim 29 wherein the acid is a member of the group consisting of hydrochloric, hydrochloric, phosphoric, citric, sulfuric and acetic acids.
Claim 45
Dependent Claim
25 words
A method according to claim 37 wherein the acid is a member of the group consisting of hydrochloric, hydrofluoric, phosphoric, citric, sulfuric and acetic acids.
Claim 46
Dependent Claim
13 words
A method according to claim 24 wherein the oxidizing agent is hydrogen peroxide.
Claim 47
Dependent Claim
13 words
A method according to claim 29 wherein the oxidizing agent is hydrogen peroxide.
Claim 48
Dependent Claim
13 words
A method according to claim 37 wherein the oxidizing agent is hydrogen peroxide.
Claim 49
Dependent Claim
20 words
A method according to claim 24 wherein said developer solution in step (c) is aqueous sodium hydroxide or sodium carbonate.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1996-08-02 | 1997-02-01 | 1997-08-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2000-08-02 | 2001-02-01 | 2001-08-03 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2004-08-02 | 2005-02-01 | 2005-08-03 | $7700.00 | Window Closed / Lapsed |