CA1325791C - Method and coating material for applying electrically conductive printed patterns to insulating substrates - Google Patents
Method and coating material for applying electrically conductive printed patterns to insulating substratesInfo
- Publication number
- CA1325791C CA1325791C CA 554456 CA554456A CA1325791C CA 1325791 C CA1325791 C CA 1325791C CA 554456 CA554456 CA 554456 CA 554456 A CA554456 A CA 554456A CA 1325791 C CA1325791 C CA 1325791C
- Authority
- CA
- Canada
- Prior art keywords
- coating agent
- metal
- substrate
- carrier substance
- approximately
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 94
- 239000000758 substrate Substances 0.000 title claims abstract description 86
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 13
- 238000000576 coating method Methods 0.000 title abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- 239000000126 substance Substances 0.000 claims abstract description 48
- 238000001465 metallisation Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 238000004873 anchoring Methods 0.000 claims abstract description 10
- 230000005855 radiation Effects 0.000 claims abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 229910052763 palladium Inorganic materials 0.000 claims description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 239000007767 bonding agent Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010970 precious metal Substances 0.000 claims description 8
- 239000006233 lamp black Substances 0.000 claims description 7
- 229910000923 precious metal alloy Inorganic materials 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000008262 pumice Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004831 Hot glue Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001289 polyvinyl ether Polymers 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000013032 Hydrocarbon resin Substances 0.000 claims 1
- 229920006270 hydrocarbon resin Polymers 0.000 claims 1
- 239000011133 lead Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000004020 conductor Substances 0.000 description 37
- 239000003054 catalyst Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 7
- 239000011888 foil Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920006112 polar polymer Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- -1 polyphenylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/398—Processes based on the production of stickiness patterns using powders
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
- C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
- H05K3/185—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method by making a catalytic pattern by photo-imaging
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0129—Thermoplastic polymer, e.g. auto-adhesive layer; Shaping of thermoplastic polymer
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/10—Using electric, magnetic and electromagnetic fields; Using laser light
- H05K2203/107—Using laser light
Abstract
ABSTRACT OF THE DISCLOSURE
A method and coating material for applying electrically conductive printed patterns to insulating substrates is provided. The coating material includes a non-metallic, grainy carrier substance having metal of the oxidation degree 0 applied thereto. An energy radiation source, particularly of a deflectable laser beam, is used to secure anchoring of the carrier substance to the substrate in the region of the desired printed pattern. As a consequence of a three-dimensional arrangement of the metal, a three-dimensional nuclei distribution is produced that leads to a reliable and fast metallization of the printed pattern on the basis of chemical metal deposition.
The method of the invention is especially suited for laser pattern transfer for the manufacture of printed circuit boards.
A method and coating material for applying electrically conductive printed patterns to insulating substrates is provided. The coating material includes a non-metallic, grainy carrier substance having metal of the oxidation degree 0 applied thereto. An energy radiation source, particularly of a deflectable laser beam, is used to secure anchoring of the carrier substance to the substrate in the region of the desired printed pattern. As a consequence of a three-dimensional arrangement of the metal, a three-dimensional nuclei distribution is produced that leads to a reliable and fast metallization of the printed pattern on the basis of chemical metal deposition.
The method of the invention is especially suited for laser pattern transfer for the manufacture of printed circuit boards.
Description
1325~
BACKGROUND OF THE INVEN~ION
The present invent~ on relates generally to a method of applying electrlcally conductiva printed patterns to electrically insulating ~ubstrates. More particularly, the present invention relates to a method of applying electrically conductive printed patterns, particularly conductor patterns~ to electrically insulating substrates, whereby a metal-containing coating agent is transferred onto the ~ubstrate in an arrangement corresponding to the printed pattern to be generated. The coating agent is transferred under the influence of energy radiation, and is chemically metallized. The present invention also relates to a metal-containing coating agent for the appllcation of such printed patterns to electrically insulating substrates.
German periodical "~alvanotechnik" 77 (1986) No. 1 t pages 51 through 60, discloses a method for applying conductor patterns to electrically conductive (SIC) substrates wherein the transfer of the conductor pattern is undertaken with the assistance of a laser. To this end, adhesive-coated epoxy resin base material is employed as a substrate. This substrate is subjected to pretreatment with S03 vapor phase etching with a NH3 etching stop for roughening the adhasive. A Cr (III) photosensitizer which contains chrome (III)-chloride, sodium oxalate and palladium ( II )-chloride, for example, is then applied to *he substrate as a metal-containing coating agent. Pd nuclei is generated in the region o~ the conductor pattern in the ollowing laser image transfer, these Pd nuclei enabling a chemical or galvanic thick copper-plating after a pre-metallization with Ni-P and a haat treatmant at 100 to about 120C. Due to a thick copper-plati~g ln copper baths working without external current and given lonyer exposition times, - 2 - ~.
. - ,. , .. - , . - . - -~3~7~
disociations of the adhesive layer from the base material can occur so that the deposited interconnects lose thair adhesive foundation.
"IBM Technical Disclosure Bulletin", VolO 15, No. 9, February 1973, page 2855, discloses a method for applying conductor patterns to ceramlc ~ubstrates. The method includes applying to a green ceramic substrate a metal-contalning thermoplastic powder that is subsequently exposed to a laser beam ln accord with the desired conductor pattern. The laser beam melts the thermoplastic powder embedding and adhering the metal particles to the ceramic substrate. RPmaining metal-containing powder that was not exposed to the laser beam can then be removed with an air ~et.
These prior methods have not been entirely satisfactory. In producing conductor patterns on a substrate, numerous considerations must be taken into account. It is desirable to reduce the exposition time. Further, it is necessary for the electrically conductive pattern to be sufficiently ~nchoredO Some previous methods of producing conductor patterns on a substrate have not been entirely satisfactory because they utilize decomposition raactions that produce environmental pollution. Some previous methods of producing these conductor pat*erns suffer the disadvantage of being costly.
There is therefore a need for an improved method of producing conductor patterns on a substrate, as well as an improved metal~-contalning coating agent for the application of such printed patterns of a substrate.
- 132~7~
20365-~779 SUMMARY OF THE INVENTION
The present invention provides an improved method for applying electrically conductive printed patterns, particularly conductor patterns, to electrically insulatlng substrates. The method enables a simple transfer of the printed pa~tern and, particularly in the manufacture of prin~ed circuit boards, guarantees the production o~ extremely fine conductor structures having an adequate adhesive foundation. The present invention further provides a metal-containing coating agent suitable for being applied to substrates to create a desired conductor pattern.
Thus, according to one aspect, the invention provides a method for applying electrically conductive printed patterns to insulating substrates wherein a metal-containing coating agen~ is transferred onto a substrate under the influence of energy radiation in a prlnted pattern to be produced and is chemically me~allized, the coating agent includes a non metallic grainy carrier substance having metal of the oxidation degree O applied thereto.
According to another aspect, the invention provides a metal-containing coating agent for applying electrically conductive printed patterns onto electrically insulating sub~trates comprising a non-metallic, grainy carrier to which is applied metal in the oxidation degree 0.
~ 3 2 ~ 7 9 ~ ~0365-2779 According to still another aspect, the invention provides a metal-containing coating agent for applying electrically conductive printed patterns to electrically insulating substrates comprising:
a non-metallic, grainy carrier substance consisting of at least one compound chosen from the group consisting of:
activated carbon; conductive lampblack; calcium carbonate;
diatomaceous earth; bentonite; kaolin; silica gel; aluminum oxide;
titanium oxide; plastic; and pumice stone; and a metal in the oxidation degree 0 that is applied to the carrier substance, the metal consisting of a compound chosen ~rom the group consisting of: precious metals; precious metal alloys;
and precious metal alloys with non-precious metals chosen from the group consisting of zinc, nickel, tin, and copper.
In an embodiment of the present invention, the coating material comprises a non-metallic, grainy carrier substance with metal of the oxidation degree 0 applied thereon.
The present invention is based, in part, on the discovery that the decomposition of metallo-organic compounds, induced by energy radiation, can be avoided by employing metal of the oxidation degree 0, insofar as the metal can be prepared in a way that is suitable for the transfer of the printed pattern and for the firm anchoring on or in the substrate. This preparation of metal having the oxidation degree 0 ensues by utilizing a non-metallic grainy carrier substance on which the metal is applied in a finely distributed form. Such carrier substances for metals of -~a-` .
.. ..
~32~
the oxidation degree 0 are known and are referred to as carrier catalysts which, for example, are utilized by hydration or dehydration. In the manufacture of such carrier catalysts, catalytic metals such as platinum, palladium, and nickel are precipitated on ca~alyst carriers such as activated carbon, diatomaceous earth, bentonite, kaolin, silica gel, aluminum oxide, and pumice stone. Commercially available carrier -~b-~32~7~1 catalysts generally contain between approximately 0.5 to about 60 weight percent metal.
As a result of utilizing the coating agent of the present inventlon, a three-dimensional d$stribution of the metal nuclei is produced on the substrate. This three-dimensional distribution promotes chemical metallization and considerably reduces the exposition times in the corresponding baths working without e~ternal current. Further, the grainy carrier substances of the coating agent of the present invention afford a very good anchoring in the substrate which is controllable through the use of energy radiation. The anchoring guarantees an excellent adhesive foundation for the interconnects in, for example, the manufacture of printed circuit boards.
The present invention provides as a further advantage reduced environmental pollution due to the elimination of the previously required decomposition reactions. The present inv~ntion also affords a more economical process for applying electrically conductive printed patterns to substrates due to the simplification of the process, and tha ability to proces~ the coating material in liquid form. The ability to process the coating material in liquid form is achieved because the metals bonded to the carrier substances can be dispersed very well in liquids and lead to stable liquid coa*ing agentsO
The present invention also provides a metal-containing coating agent for applying electrically conductive printed patterns, particularly conductor patterns to electrically insulating substrates. The metal, in the metal-containing coating, is in the oxidation degree 0 and is applie~ to a non-metallic, grainy carrier substance. The above stated advantages '. ~' !
2~7~
are achieved by employln~ the ooating agent of the present invention in the pattern transfar with energy beams.
The method and ~oatin~ agent of the present lnvention fundamentally enables ~ multltude of procesc$ng and transfer forms. Thus, the ooating agent can be utilized ln Rolid form as a powder wlth or without 2 bonding ~gent, in a llquld form, or in the form of a foll to be applled to the surface of ~ ~ubstrate.
The foil can be composed only of tha coating agent or can be composed of the coating agent and of sn auxiliary carrier. If a foil ls used, the trans~er of the printed patterns with the foil can proceed, for example, a set forth in French Published Applicatlon No. 2 250 318.
Pursuant to the method of the present invention, the printed patterns can be transferred, through the use of energy radiation, in a variety of manners. In addition to the utili~ation of masks, dies and the like, the printed patterns can also be produced by relative movements between energy beam and substrate. It should be noted that the term "trans~er of printed patterns" includes the sur~ace-wide metallizations of substrates. In this embodiment, subtractive techniques can also be utilized.
Additional features and advantages of the present invention are dascribed in, and will be apparent from, the detailed description of the presently preferred embodiments and from the drawings.
BREIF DESCRIPTION OF THE DRAWINGS
Figure 1 illustrates a ~chematic representation of an embodiment of the method of the present invention.
:i .
, . . . . . . .
132~
~ lgure 2 illustrates a cross-sectional perspectlve view of the coating agent of the present invention ~pplled to the substrate.
~ igure 3 lllustrates a cross-sectional perspective view of the substrate of ~igure 2 having the carrier substance of the coating agent anchored therein.
Figure 4 illustrates a cross-sectional perspective view of the conductor pattern transferred via the steps illustrated in Figures 2 and 3 and anchored in the substrate.
~ igure 5 illustrates a cross-sectional view of the conductor pattern of Figure 4 following a chemical and galvanic metallization.
Figure 6 illustrates a cross-sectional perspective view of an embodiment of the present lnvention wherein the ooating agent contains a hot-melt adhesive as a bonding agent.
Figure 7 illustrates a cross-sectional perspective view o~ the anchoring of the conductor pattern in the substrate of Figure 6.
DETAILED DESCRIPTION OF THE PRESENTLY P~EFERRED EMBODIMENTS
The present invention provides an improved method for applying electrically conductive printed patterns to insulating substrates. The present invention also provides a coating material for applying electrically conductive printed patterns *o insulating substrates.
~ igure 1 illu-~trates a highly simplified, schematic illustration of the present invention for transferring a conductor pattern onto a substrate. The substrate S can be, for example, composed of a thermoplastic synthetic. The illustrated substrata S is a portion of the base material for an in~ection molded printed circuit board. High-temperature-resistant 4'"~
~32~7~
thermoplastics such as, foF example, polyetherimide, polyethersulfone, polyphenylene~ulfide, and li~uid crystal polymers are particularly suitable às materials for such base materials.
Pursuant to the method of the present invention, a coating agent is applied to the surface o~ the substrate S. The coating agent includes a gra~ny carrier substance T that is indicated by tiny dots in Figure 1. In an embodiment of the present invention, preferably, the coating agent is applied to the surface of the substrate S in a layer thickness of approximately 4 microns.
As illustrated, a laser ~a is utilized as an energy beam. The laser La generates a laser beam L in whose beam path a photographic shutter Fv, a first rotatable deflecting mirror Asx of a deflection optics Ao, a second rotatable deflectin~ mirror Asy of the deflection optics Ao, and an objective O are successively arranged. The mirrors Asx and Asy function to focus the laser beam onto the surface of the substrate S. The position of the substrate S is determined with reference to a planar, Cartesian x, y coordinate system. Accordingly, the first deflecting mirror Asx of the deflection optics Ao functions to deflect the laser beam L in the horizontal direction ~; this is indicated in Figure 1 by arrows x'. The second deflecting mirror Asy of the deflection optics ~o funct1ons to deflect the laser beam L in the vertical dirsction y; this is indicated in Figure 1 by arrow y'.
To control the deflecting mirrors Asx and Asy, a microcomputer Mc that has an input E is utilized. The microcomputer Mc therefore determines the conductor pattern to be produced on the substrater The lines for the control of the 132~7~
deflecting mirrors Asx and Asy are indicated by Lex and Ley, respectively. The microcomputer Mc also ~ontrols the photographic shutter Fv; this i~ $ndicated by a corresponding line Le.
A variety of lasers La can be utilized ln the present invention. For example, the laser La can be a C02 laser which is utilized in continuous wave mode or which can also be electronically pulsed, whereby the mean power lies between approximately 0.5 watts to about 8 watts. The laser La can also be, for example, a Nd-YAG laser having a mean power between approximately 0.2 watts to about 50 watts. The focussing of the laser beam L is adjustable, whereby the diameter of the laser beam L at the substrate surface can be set to diameters of between approximately 50 microns to about 400 microns.
For transferring the conductor pattern to the substrate S, printing ink applied thereto is swept by the laser beam L, in accord with the interconnect configuration lnput, into the microcomputer Mc via the input E. The trace of the laser beam L
in the transfer of the conductor pattern is illustrated in Figure 1 as interconnect ~b. Further details of the transfer of conductor patterns through the method of the present invention will now be set forth in graater detail below with reference to Figures 2 through 5.
Figure 2 ~llu~trates a hi~hly simplified, schematic illustration of a substrate S on whose surface the individual particles of the carrier substance T of the coating agent are uniformly distributed. As illustrated, the coating agent includes individual particles of metal M that are carried by the surface of the carr1er substance T. Preferably, the carrier substance T is: activated carbon; conductive lamp black; calcium _ g _ `'- 'l~j _.
~2~
carbonate; diatomaceous earth; bentonite; kaolin; plastic; silica gel; aluminum oxide; titinlum Gxide; or pumice stone - either alone or in combi~ation. Preferably, the metal M i5 chosen from the group of precious metals. In an embodiment, the metal is a precious metal alloy with a non-precious metal selected from the group consisting of: lead; ~inc; nickel; tin; and copper.
As stated above, a laser beam L is used to create the conductor pattern on the substrate. To this end, the laser beam L is guided over the sur$ace of the substrate S in the conductor pattern desired to be produc0d. The laser beam L creates a superficial melting of the substrate. As illustrated in Figure 3, this melting effects a securs anchoring of the carrier substance T in the region of the desired conductor image.
After the meltiny by the laser beam L, non-anchored carrier substancs T is removsd by brushing, spraying, or rinsing in an ultrasound bath or the like~ Accordingly, as lllustrated in Figure 4, only anchored carrier substance T in the region of the conductor pattern to be produced remains on the substrate S~ After removal of the non-anchored carrier substance T, the particles of metal M, present in a three-dimensional distribution on the anchored carrisr substance T, serve as nuclei for the chemical metallization of the conductor pattern executsd without external current. Therefore, the conductor pattern can be completely constructed by chemical metal deposition or by chemical and subseguent galvanic metal deposition.
Figure 5 illustrates the construction of the conductor pattern by chemic~l and subsequent galvanlc mstal deposition. In Figure 5, the chemically deposited metal is referenced by CM and the galvanically deposited metal is referenced by GM. In an embodiment of the present invention, preferably, copper is . ~ .
.
3~32~7~1 utilized for the chemically and galvanically deposited metals CM
and GM, respectively.
Figures 6 and 7 illustrate another embodlment of the method of the present invention. In this embodlm2nt, the carrier substance T is saturated with ~ hot-melt adhesive ~s the bond$ng sgent. This bonding agent then melts under the influence of the laser beam L and, as illustrated ln Fi~ure 6, leads to a gluing of the carrier substance T to the surface of the substrate S.
In this embodiment, preferably a tharmoplastic synthetic is again utilized as the substrate S. A heat-treatment can be carried out after the removal of the unglued carrier substance T. This he~t-treatment, as illustrated ln Figure 7, leads to a fusing into the substrate surface and an even better anchoring of the carrier substance T in the region of the desired conductor pattern.
By way of example, microwaves can be used for the heat-treatment step. Polar polymers having a high dielectric constant have been found to function satis~actorily as the bonding a~ent with microwaves. When polar polymers with a high dielectric constant are utilized as the bonding agent, the microwaves will only influence the substrate. Accordingly, with microwaves a deformation of the substrate occasioned by the heat-treatment can be reliably suppressed.
Preferably, the bonding agent comprises at least one compound chosen from the group consisting of: polyamides;
polyimides; colophonium resins; hydrocarbon reslns; ketone resins; polyvinylether; maleic resin; and polyvinyl buteral. In an embodiment of the method of the present ln~ention, preferably, polyamide and polyimide are utilized as the polar polymers for the bonding agent to be treated with microwaves.
132~
By way o example, and not limitat~on, examples of the method and coatin~ of the present invention will now be ~iven.
Example 1 A coatlng agent in accordance wlth the present invention was made as follows. A carrier catalyst composed of activated carbon hav~ng palladium applled thereto was utilized.
Approximately 10 weight percent palladium was distr$buted on approximately 90 weight percent activated carbon. The activated carbon having the palladium applled thereto was present in fine-grained form. Approximately 30 percent of the grains had a grain size below 10 microns; approximately 85 percent of the grains had a grain size under 50 microns; and approximately 98 percent of the grains had a grain size under 100 micronsO
The coating agent manufactured therewith contained the following constituents: approximataly 30 weight percent activated carbon plus palladium; approximately 2 weight percent yellow pigment; approximately 25 to about 30 weight peroent bonding agent; approximately 1.5 weight percent of a thix~troping agent;
and the remainder of the coating agent consisted of a solvent.
Although ethanol was used as the s~lvent, the solvent can include at least one organic solvent chosen from $he group consisting of: alcohols; esters; ketones; and hydrocarbons both aliphates and aromatics. A mixture of maleic resin and polyvinyl butyral was used as the bonding agent.
The coating agent described abovs, was applied to a substrate of polyethersulphone by immers~on. The transfer of a conductor pattern was carried out utilizing the process illustrated in Figure 1 with the assistance of 8 laser beam.
Subsequently, the excess coating agent was removed in an ultrasound cleaning bath utilizing isobutyl methylketone as the .:~ .., 11 32~7~
cleaning fluid. The conductor pattern was then built up through copper depos~tion working without axternal current. The copper was built up to a layer thickness of approxlmately 2 microns.
The conductor pattern was then built up through galvanlc copper deposition, being built up therewlth to a layer thickness of approximately 33 microns to produce an electrically conductive prlnted pattern on the substrate.
Example 2 In this example, the steps and procedures ~et forth above for example 1 were carried out except tha activated carbon with the palladium applied thereto was replaced by a fin~r-grained substance of carbon with palladium having a mean grain size of about 4 microns. The resultant coating agent was then applied to tha substrate by being sprayed on the substrate to a layer thickness of approximately 4 to about 5 microns to produce an electrically conductive printed pattern on the substrate.
Example 3 In this example, the steps and procedures set forth in example 2 above were followed except calcium carbonate was substituted for the activated carbon ln the evating agent.
Example 4 In this example, the steps and procedures set forth in example 2 above were followed except the ratio of the activated carbon to palladium in the coating agent was modified. Instead of the weight ratlo of approximately 10 weight percent palladium to approximately 90 wei`ght percent activated zarbon, approximately 97 weight percent of activated carbon was utilized as the carrier to approximately 3 weight percent of palladium.
.. . .
~32~7~
Example 5 In thi~ example, the steps and procedures set ~orth in example 3 were followed, however, the weight ratio of calcium carbonate to palladium was modificd. Instead of the weight ratio of approximately 10 weight percent palladium to &pproximately 90 weight percent calcium carbonate, approximately 97 weight percent of calcium carbonate served as the carrier for approximately 3 weight percent palladium.
Example 6 In this example, the steps and procedures of example 4 were followed except platinum was substituted for the palladium used in the coating agent of example 4.
Example 7 In this example, tha steps and procedures of example 5 were followed except platinum was substituted for the palladium used in the coating agent of example S.
Example 8 In this example, the steps of example 1 were followed, however, after the removal of the excess coatlng agent an after-treatment in an ammonia chloride bath was performed. This after-treatment led to a significant improvement in the adhesion of the interconnects to the ~ubstrate.
The after-treatment with a suitable bath can also be utilized in the methods set forth in examples 2 through 7. In utilizing the after-treatment with the steps and method of example 2, the after-treatment with ammonia chloride led to an adhesion of the interconnects of about 1 N/nm2.
Example 9 In this example, the steps and procedures of example 1 were followed, however, the activated carbon of the coating agent , ~3~7~
was replaced by conductive-lampblack. Whereas irregularlties in the interconnect ~tructure can occur when activated carbon is utilized, when the grai~ is excessively large because of the electrically non-conductive characteristic of the carbon, the conductivity continues to exist at this location as a result of the use of conductlve lampblack; even though the conductivity is 10ss than in the case of metals. The conductive lampblack thus does not replace the metal. Rather, it augments the function of the metals as nuclei for the following, ¢urrentless metallization.
Example 10 In this example, the steps and procedures of example 1 were followed~ but the activated carbon of the coating agent in example 1 was replaced by a plastic on an acrylate basis.
Example 11 In this example, the steps and proceduras of example 1 were followed, however, the activated carbon of the coating agent was replaced by the plastic compound of the substrate. For example, given a substrate and carrier composed of polyetherimide, an extremely high adhes~on of the interconnects to the substrate was achieved.
Example 1~
Following the steps and procedures of example 1, a powdery coating agent composed only of the carrier catalyst, i.e., of activated carbon and palladium, was used. This coating agent was strewn onto the substrate, and was anchored with a laser beam ln~accordance with the conductor pattern. The substrate and coating agent was then chemically and, as needed, galvanically copper-plated~ ~he soldering of the substrate was thereby improved.
~32~7~
Example 13 In this example, the ~taps and procedures of example 1 were followed, however, the ooating agent was first applied to a foil that served ~s ~n lntermadiate carrier. The foil was then placed onto the substrate, whereupon the conductor pattern was transferred onto the substrate through the foil with a laser.
Example 14 In this example, the steps and procedures of example 1 were followed, but, the activated carbon of the coating agent was replaced by a plastic-bonded catalyst.
Example 15 In this example, the steps and procedures of example 14 were followed except a ground lon exchanger was used as a plastic-bonded catalyst, a palladium (salt) solution having been introduced thereinto and the palladium having been subsequently chemically reduced to O-valent palladium.
Example 16 In this example, the steps and procedures of example 14 were follo~ed, but, a ground expanded polymer having a large surface was used as a plastic-bonded catalyst, the palladium having been deposited thereon. The expanded polymer to bs utilized can e~ther be open-celled or closed-celled.
Example 17 In this example, the steps and procedures of example 14 were followed, but, a polymer-bonded palladium catalyst was used as a plastic-bonded catalyst~ The palladium can be bonded chelate-like or salt-like, such as polyamines or polyacrylic acid, and can be reduced on the polymer to O-valent palladium.
The resultant product can still be subsequently soluble and can then be applied to the substrate as a solution. If the resultant ~` ~3~7~
product is insoluble, it can first be ground and then be applied to the substrate.
Sediment grlnding can be utilized for grinding the plastics to form mlcron-sizad partlcles given the utilization of plastic-bonded oatalysts. The polymers are then m$xed with an inorganic ~alt. The polymers, due to electro-statlc charging, would adhere to one another if the salt was not present. The salt prevents the adheslon of the polymers to one another and is in turn dissolved out with water after the grinding.
It should be noted that the anchoring of the conductor pattArn on the substrate can be potentially enhanced through the u5e of heat. For example, given the employment of substrates composed of polyetherim~de, ~uch a tempering step performed after the galvanic copper-plating increased the adhesion of tha conductor pattern to the substrate by up to 50 percent.
It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present lnvention and without diminishing its attendant advantages. It is thereby intended that such changes and modifications be covered by the appended claims.
, . .
BACKGROUND OF THE INVEN~ION
The present invent~ on relates generally to a method of applying electrlcally conductiva printed patterns to electrically insulating ~ubstrates. More particularly, the present invention relates to a method of applying electrically conductive printed patterns, particularly conductor patterns~ to electrically insulating substrates, whereby a metal-containing coating agent is transferred onto the ~ubstrate in an arrangement corresponding to the printed pattern to be generated. The coating agent is transferred under the influence of energy radiation, and is chemically metallized. The present invention also relates to a metal-containing coating agent for the appllcation of such printed patterns to electrically insulating substrates.
German periodical "~alvanotechnik" 77 (1986) No. 1 t pages 51 through 60, discloses a method for applying conductor patterns to electrically conductive (SIC) substrates wherein the transfer of the conductor pattern is undertaken with the assistance of a laser. To this end, adhesive-coated epoxy resin base material is employed as a substrate. This substrate is subjected to pretreatment with S03 vapor phase etching with a NH3 etching stop for roughening the adhasive. A Cr (III) photosensitizer which contains chrome (III)-chloride, sodium oxalate and palladium ( II )-chloride, for example, is then applied to *he substrate as a metal-containing coating agent. Pd nuclei is generated in the region o~ the conductor pattern in the ollowing laser image transfer, these Pd nuclei enabling a chemical or galvanic thick copper-plating after a pre-metallization with Ni-P and a haat treatmant at 100 to about 120C. Due to a thick copper-plati~g ln copper baths working without external current and given lonyer exposition times, - 2 - ~.
. - ,. , .. - , . - . - -~3~7~
disociations of the adhesive layer from the base material can occur so that the deposited interconnects lose thair adhesive foundation.
"IBM Technical Disclosure Bulletin", VolO 15, No. 9, February 1973, page 2855, discloses a method for applying conductor patterns to ceramlc ~ubstrates. The method includes applying to a green ceramic substrate a metal-contalning thermoplastic powder that is subsequently exposed to a laser beam ln accord with the desired conductor pattern. The laser beam melts the thermoplastic powder embedding and adhering the metal particles to the ceramic substrate. RPmaining metal-containing powder that was not exposed to the laser beam can then be removed with an air ~et.
These prior methods have not been entirely satisfactory. In producing conductor patterns on a substrate, numerous considerations must be taken into account. It is desirable to reduce the exposition time. Further, it is necessary for the electrically conductive pattern to be sufficiently ~nchoredO Some previous methods of producing conductor patterns on a substrate have not been entirely satisfactory because they utilize decomposition raactions that produce environmental pollution. Some previous methods of producing these conductor pat*erns suffer the disadvantage of being costly.
There is therefore a need for an improved method of producing conductor patterns on a substrate, as well as an improved metal~-contalning coating agent for the application of such printed patterns of a substrate.
- 132~7~
20365-~779 SUMMARY OF THE INVENTION
The present invention provides an improved method for applying electrically conductive printed patterns, particularly conductor patterns, to electrically insulatlng substrates. The method enables a simple transfer of the printed pa~tern and, particularly in the manufacture of prin~ed circuit boards, guarantees the production o~ extremely fine conductor structures having an adequate adhesive foundation. The present invention further provides a metal-containing coating agent suitable for being applied to substrates to create a desired conductor pattern.
Thus, according to one aspect, the invention provides a method for applying electrically conductive printed patterns to insulating substrates wherein a metal-containing coating agen~ is transferred onto a substrate under the influence of energy radiation in a prlnted pattern to be produced and is chemically me~allized, the coating agent includes a non metallic grainy carrier substance having metal of the oxidation degree O applied thereto.
According to another aspect, the invention provides a metal-containing coating agent for applying electrically conductive printed patterns onto electrically insulating sub~trates comprising a non-metallic, grainy carrier to which is applied metal in the oxidation degree 0.
~ 3 2 ~ 7 9 ~ ~0365-2779 According to still another aspect, the invention provides a metal-containing coating agent for applying electrically conductive printed patterns to electrically insulating substrates comprising:
a non-metallic, grainy carrier substance consisting of at least one compound chosen from the group consisting of:
activated carbon; conductive lampblack; calcium carbonate;
diatomaceous earth; bentonite; kaolin; silica gel; aluminum oxide;
titanium oxide; plastic; and pumice stone; and a metal in the oxidation degree 0 that is applied to the carrier substance, the metal consisting of a compound chosen ~rom the group consisting of: precious metals; precious metal alloys;
and precious metal alloys with non-precious metals chosen from the group consisting of zinc, nickel, tin, and copper.
In an embodiment of the present invention, the coating material comprises a non-metallic, grainy carrier substance with metal of the oxidation degree 0 applied thereon.
The present invention is based, in part, on the discovery that the decomposition of metallo-organic compounds, induced by energy radiation, can be avoided by employing metal of the oxidation degree 0, insofar as the metal can be prepared in a way that is suitable for the transfer of the printed pattern and for the firm anchoring on or in the substrate. This preparation of metal having the oxidation degree 0 ensues by utilizing a non-metallic grainy carrier substance on which the metal is applied in a finely distributed form. Such carrier substances for metals of -~a-` .
.. ..
~32~
the oxidation degree 0 are known and are referred to as carrier catalysts which, for example, are utilized by hydration or dehydration. In the manufacture of such carrier catalysts, catalytic metals such as platinum, palladium, and nickel are precipitated on ca~alyst carriers such as activated carbon, diatomaceous earth, bentonite, kaolin, silica gel, aluminum oxide, and pumice stone. Commercially available carrier -~b-~32~7~1 catalysts generally contain between approximately 0.5 to about 60 weight percent metal.
As a result of utilizing the coating agent of the present inventlon, a three-dimensional d$stribution of the metal nuclei is produced on the substrate. This three-dimensional distribution promotes chemical metallization and considerably reduces the exposition times in the corresponding baths working without e~ternal current. Further, the grainy carrier substances of the coating agent of the present invention afford a very good anchoring in the substrate which is controllable through the use of energy radiation. The anchoring guarantees an excellent adhesive foundation for the interconnects in, for example, the manufacture of printed circuit boards.
The present invention provides as a further advantage reduced environmental pollution due to the elimination of the previously required decomposition reactions. The present inv~ntion also affords a more economical process for applying electrically conductive printed patterns to substrates due to the simplification of the process, and tha ability to proces~ the coating material in liquid form. The ability to process the coating material in liquid form is achieved because the metals bonded to the carrier substances can be dispersed very well in liquids and lead to stable liquid coa*ing agentsO
The present invention also provides a metal-containing coating agent for applying electrically conductive printed patterns, particularly conductor patterns to electrically insulating substrates. The metal, in the metal-containing coating, is in the oxidation degree 0 and is applie~ to a non-metallic, grainy carrier substance. The above stated advantages '. ~' !
2~7~
are achieved by employln~ the ooating agent of the present invention in the pattern transfar with energy beams.
The method and ~oatin~ agent of the present lnvention fundamentally enables ~ multltude of procesc$ng and transfer forms. Thus, the ooating agent can be utilized ln Rolid form as a powder wlth or without 2 bonding ~gent, in a llquld form, or in the form of a foll to be applled to the surface of ~ ~ubstrate.
The foil can be composed only of tha coating agent or can be composed of the coating agent and of sn auxiliary carrier. If a foil ls used, the trans~er of the printed patterns with the foil can proceed, for example, a set forth in French Published Applicatlon No. 2 250 318.
Pursuant to the method of the present invention, the printed patterns can be transferred, through the use of energy radiation, in a variety of manners. In addition to the utili~ation of masks, dies and the like, the printed patterns can also be produced by relative movements between energy beam and substrate. It should be noted that the term "trans~er of printed patterns" includes the sur~ace-wide metallizations of substrates. In this embodiment, subtractive techniques can also be utilized.
Additional features and advantages of the present invention are dascribed in, and will be apparent from, the detailed description of the presently preferred embodiments and from the drawings.
BREIF DESCRIPTION OF THE DRAWINGS
Figure 1 illustrates a ~chematic representation of an embodiment of the method of the present invention.
:i .
, . . . . . . .
132~
~ lgure 2 illustrates a cross-sectional perspectlve view of the coating agent of the present invention ~pplled to the substrate.
~ igure 3 lllustrates a cross-sectional perspective view of the substrate of ~igure 2 having the carrier substance of the coating agent anchored therein.
Figure 4 illustrates a cross-sectional perspective view of the conductor pattern transferred via the steps illustrated in Figures 2 and 3 and anchored in the substrate.
~ igure 5 illustrates a cross-sectional view of the conductor pattern of Figure 4 following a chemical and galvanic metallization.
Figure 6 illustrates a cross-sectional perspective view of an embodiment of the present lnvention wherein the ooating agent contains a hot-melt adhesive as a bonding agent.
Figure 7 illustrates a cross-sectional perspective view o~ the anchoring of the conductor pattern in the substrate of Figure 6.
DETAILED DESCRIPTION OF THE PRESENTLY P~EFERRED EMBODIMENTS
The present invention provides an improved method for applying electrically conductive printed patterns to insulating substrates. The present invention also provides a coating material for applying electrically conductive printed patterns *o insulating substrates.
~ igure 1 illu-~trates a highly simplified, schematic illustration of the present invention for transferring a conductor pattern onto a substrate. The substrate S can be, for example, composed of a thermoplastic synthetic. The illustrated substrata S is a portion of the base material for an in~ection molded printed circuit board. High-temperature-resistant 4'"~
~32~7~
thermoplastics such as, foF example, polyetherimide, polyethersulfone, polyphenylene~ulfide, and li~uid crystal polymers are particularly suitable às materials for such base materials.
Pursuant to the method of the present invention, a coating agent is applied to the surface o~ the substrate S. The coating agent includes a gra~ny carrier substance T that is indicated by tiny dots in Figure 1. In an embodiment of the present invention, preferably, the coating agent is applied to the surface of the substrate S in a layer thickness of approximately 4 microns.
As illustrated, a laser ~a is utilized as an energy beam. The laser La generates a laser beam L in whose beam path a photographic shutter Fv, a first rotatable deflecting mirror Asx of a deflection optics Ao, a second rotatable deflectin~ mirror Asy of the deflection optics Ao, and an objective O are successively arranged. The mirrors Asx and Asy function to focus the laser beam onto the surface of the substrate S. The position of the substrate S is determined with reference to a planar, Cartesian x, y coordinate system. Accordingly, the first deflecting mirror Asx of the deflection optics Ao functions to deflect the laser beam L in the horizontal direction ~; this is indicated in Figure 1 by arrows x'. The second deflecting mirror Asy of the deflection optics ~o funct1ons to deflect the laser beam L in the vertical dirsction y; this is indicated in Figure 1 by arrow y'.
To control the deflecting mirrors Asx and Asy, a microcomputer Mc that has an input E is utilized. The microcomputer Mc therefore determines the conductor pattern to be produced on the substrater The lines for the control of the 132~7~
deflecting mirrors Asx and Asy are indicated by Lex and Ley, respectively. The microcomputer Mc also ~ontrols the photographic shutter Fv; this i~ $ndicated by a corresponding line Le.
A variety of lasers La can be utilized ln the present invention. For example, the laser La can be a C02 laser which is utilized in continuous wave mode or which can also be electronically pulsed, whereby the mean power lies between approximately 0.5 watts to about 8 watts. The laser La can also be, for example, a Nd-YAG laser having a mean power between approximately 0.2 watts to about 50 watts. The focussing of the laser beam L is adjustable, whereby the diameter of the laser beam L at the substrate surface can be set to diameters of between approximately 50 microns to about 400 microns.
For transferring the conductor pattern to the substrate S, printing ink applied thereto is swept by the laser beam L, in accord with the interconnect configuration lnput, into the microcomputer Mc via the input E. The trace of the laser beam L
in the transfer of the conductor pattern is illustrated in Figure 1 as interconnect ~b. Further details of the transfer of conductor patterns through the method of the present invention will now be set forth in graater detail below with reference to Figures 2 through 5.
Figure 2 ~llu~trates a hi~hly simplified, schematic illustration of a substrate S on whose surface the individual particles of the carrier substance T of the coating agent are uniformly distributed. As illustrated, the coating agent includes individual particles of metal M that are carried by the surface of the carr1er substance T. Preferably, the carrier substance T is: activated carbon; conductive lamp black; calcium _ g _ `'- 'l~j _.
~2~
carbonate; diatomaceous earth; bentonite; kaolin; plastic; silica gel; aluminum oxide; titinlum Gxide; or pumice stone - either alone or in combi~ation. Preferably, the metal M i5 chosen from the group of precious metals. In an embodiment, the metal is a precious metal alloy with a non-precious metal selected from the group consisting of: lead; ~inc; nickel; tin; and copper.
As stated above, a laser beam L is used to create the conductor pattern on the substrate. To this end, the laser beam L is guided over the sur$ace of the substrate S in the conductor pattern desired to be produc0d. The laser beam L creates a superficial melting of the substrate. As illustrated in Figure 3, this melting effects a securs anchoring of the carrier substance T in the region of the desired conductor image.
After the meltiny by the laser beam L, non-anchored carrier substancs T is removsd by brushing, spraying, or rinsing in an ultrasound bath or the like~ Accordingly, as lllustrated in Figure 4, only anchored carrier substance T in the region of the conductor pattern to be produced remains on the substrate S~ After removal of the non-anchored carrier substance T, the particles of metal M, present in a three-dimensional distribution on the anchored carrisr substance T, serve as nuclei for the chemical metallization of the conductor pattern executsd without external current. Therefore, the conductor pattern can be completely constructed by chemical metal deposition or by chemical and subseguent galvanic metal deposition.
Figure 5 illustrates the construction of the conductor pattern by chemic~l and subsequent galvanlc mstal deposition. In Figure 5, the chemically deposited metal is referenced by CM and the galvanically deposited metal is referenced by GM. In an embodiment of the present invention, preferably, copper is . ~ .
.
3~32~7~1 utilized for the chemically and galvanically deposited metals CM
and GM, respectively.
Figures 6 and 7 illustrate another embodlment of the method of the present invention. In this embodlm2nt, the carrier substance T is saturated with ~ hot-melt adhesive ~s the bond$ng sgent. This bonding agent then melts under the influence of the laser beam L and, as illustrated ln Fi~ure 6, leads to a gluing of the carrier substance T to the surface of the substrate S.
In this embodiment, preferably a tharmoplastic synthetic is again utilized as the substrate S. A heat-treatment can be carried out after the removal of the unglued carrier substance T. This he~t-treatment, as illustrated ln Figure 7, leads to a fusing into the substrate surface and an even better anchoring of the carrier substance T in the region of the desired conductor pattern.
By way of example, microwaves can be used for the heat-treatment step. Polar polymers having a high dielectric constant have been found to function satis~actorily as the bonding a~ent with microwaves. When polar polymers with a high dielectric constant are utilized as the bonding agent, the microwaves will only influence the substrate. Accordingly, with microwaves a deformation of the substrate occasioned by the heat-treatment can be reliably suppressed.
Preferably, the bonding agent comprises at least one compound chosen from the group consisting of: polyamides;
polyimides; colophonium resins; hydrocarbon reslns; ketone resins; polyvinylether; maleic resin; and polyvinyl buteral. In an embodiment of the method of the present ln~ention, preferably, polyamide and polyimide are utilized as the polar polymers for the bonding agent to be treated with microwaves.
132~
By way o example, and not limitat~on, examples of the method and coatin~ of the present invention will now be ~iven.
Example 1 A coatlng agent in accordance wlth the present invention was made as follows. A carrier catalyst composed of activated carbon hav~ng palladium applled thereto was utilized.
Approximately 10 weight percent palladium was distr$buted on approximately 90 weight percent activated carbon. The activated carbon having the palladium applled thereto was present in fine-grained form. Approximately 30 percent of the grains had a grain size below 10 microns; approximately 85 percent of the grains had a grain size under 50 microns; and approximately 98 percent of the grains had a grain size under 100 micronsO
The coating agent manufactured therewith contained the following constituents: approximataly 30 weight percent activated carbon plus palladium; approximately 2 weight percent yellow pigment; approximately 25 to about 30 weight peroent bonding agent; approximately 1.5 weight percent of a thix~troping agent;
and the remainder of the coating agent consisted of a solvent.
Although ethanol was used as the s~lvent, the solvent can include at least one organic solvent chosen from $he group consisting of: alcohols; esters; ketones; and hydrocarbons both aliphates and aromatics. A mixture of maleic resin and polyvinyl butyral was used as the bonding agent.
The coating agent described abovs, was applied to a substrate of polyethersulphone by immers~on. The transfer of a conductor pattern was carried out utilizing the process illustrated in Figure 1 with the assistance of 8 laser beam.
Subsequently, the excess coating agent was removed in an ultrasound cleaning bath utilizing isobutyl methylketone as the .:~ .., 11 32~7~
cleaning fluid. The conductor pattern was then built up through copper depos~tion working without axternal current. The copper was built up to a layer thickness of approxlmately 2 microns.
The conductor pattern was then built up through galvanlc copper deposition, being built up therewlth to a layer thickness of approximately 33 microns to produce an electrically conductive prlnted pattern on the substrate.
Example 2 In this example, the steps and procedures ~et forth above for example 1 were carried out except tha activated carbon with the palladium applied thereto was replaced by a fin~r-grained substance of carbon with palladium having a mean grain size of about 4 microns. The resultant coating agent was then applied to tha substrate by being sprayed on the substrate to a layer thickness of approximately 4 to about 5 microns to produce an electrically conductive printed pattern on the substrate.
Example 3 In this example, the steps and procedures set forth in example 2 above were followed except calcium carbonate was substituted for the activated carbon ln the evating agent.
Example 4 In this example, the steps and procedures set forth in example 2 above were followed except the ratio of the activated carbon to palladium in the coating agent was modified. Instead of the weight ratlo of approximately 10 weight percent palladium to approximately 90 wei`ght percent activated zarbon, approximately 97 weight percent of activated carbon was utilized as the carrier to approximately 3 weight percent of palladium.
.. . .
~32~7~
Example 5 In thi~ example, the steps and procedures set ~orth in example 3 were followed, however, the weight ratio of calcium carbonate to palladium was modificd. Instead of the weight ratio of approximately 10 weight percent palladium to &pproximately 90 weight percent calcium carbonate, approximately 97 weight percent of calcium carbonate served as the carrier for approximately 3 weight percent palladium.
Example 6 In this example, the steps and procedures of example 4 were followed except platinum was substituted for the palladium used in the coating agent of example 4.
Example 7 In this example, tha steps and procedures of example 5 were followed except platinum was substituted for the palladium used in the coating agent of example S.
Example 8 In this example, the steps of example 1 were followed, however, after the removal of the excess coatlng agent an after-treatment in an ammonia chloride bath was performed. This after-treatment led to a significant improvement in the adhesion of the interconnects to the ~ubstrate.
The after-treatment with a suitable bath can also be utilized in the methods set forth in examples 2 through 7. In utilizing the after-treatment with the steps and method of example 2, the after-treatment with ammonia chloride led to an adhesion of the interconnects of about 1 N/nm2.
Example 9 In this example, the steps and procedures of example 1 were followed, however, the activated carbon of the coating agent , ~3~7~
was replaced by conductive-lampblack. Whereas irregularlties in the interconnect ~tructure can occur when activated carbon is utilized, when the grai~ is excessively large because of the electrically non-conductive characteristic of the carbon, the conductivity continues to exist at this location as a result of the use of conductlve lampblack; even though the conductivity is 10ss than in the case of metals. The conductive lampblack thus does not replace the metal. Rather, it augments the function of the metals as nuclei for the following, ¢urrentless metallization.
Example 10 In this example, the steps and procedures of example 1 were followed~ but the activated carbon of the coating agent in example 1 was replaced by a plastic on an acrylate basis.
Example 11 In this example, the steps and proceduras of example 1 were followed, however, the activated carbon of the coating agent was replaced by the plastic compound of the substrate. For example, given a substrate and carrier composed of polyetherimide, an extremely high adhes~on of the interconnects to the substrate was achieved.
Example 1~
Following the steps and procedures of example 1, a powdery coating agent composed only of the carrier catalyst, i.e., of activated carbon and palladium, was used. This coating agent was strewn onto the substrate, and was anchored with a laser beam ln~accordance with the conductor pattern. The substrate and coating agent was then chemically and, as needed, galvanically copper-plated~ ~he soldering of the substrate was thereby improved.
~32~7~
Example 13 In this example, the ~taps and procedures of example 1 were followed, however, the ooating agent was first applied to a foil that served ~s ~n lntermadiate carrier. The foil was then placed onto the substrate, whereupon the conductor pattern was transferred onto the substrate through the foil with a laser.
Example 14 In this example, the steps and procedures of example 1 were followed, but, the activated carbon of the coating agent was replaced by a plastic-bonded catalyst.
Example 15 In this example, the steps and procedures of example 14 were followed except a ground lon exchanger was used as a plastic-bonded catalyst, a palladium (salt) solution having been introduced thereinto and the palladium having been subsequently chemically reduced to O-valent palladium.
Example 16 In this example, the steps and procedures of example 14 were follo~ed, but, a ground expanded polymer having a large surface was used as a plastic-bonded catalyst, the palladium having been deposited thereon. The expanded polymer to bs utilized can e~ther be open-celled or closed-celled.
Example 17 In this example, the steps and procedures of example 14 were followed, but, a polymer-bonded palladium catalyst was used as a plastic-bonded catalyst~ The palladium can be bonded chelate-like or salt-like, such as polyamines or polyacrylic acid, and can be reduced on the polymer to O-valent palladium.
The resultant product can still be subsequently soluble and can then be applied to the substrate as a solution. If the resultant ~` ~3~7~
product is insoluble, it can first be ground and then be applied to the substrate.
Sediment grlnding can be utilized for grinding the plastics to form mlcron-sizad partlcles given the utilization of plastic-bonded oatalysts. The polymers are then m$xed with an inorganic ~alt. The polymers, due to electro-statlc charging, would adhere to one another if the salt was not present. The salt prevents the adheslon of the polymers to one another and is in turn dissolved out with water after the grinding.
It should be noted that the anchoring of the conductor pattArn on the substrate can be potentially enhanced through the u5e of heat. For example, given the employment of substrates composed of polyetherim~de, ~uch a tempering step performed after the galvanic copper-plating increased the adhesion of tha conductor pattern to the substrate by up to 50 percent.
It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present lnvention and without diminishing its attendant advantages. It is thereby intended that such changes and modifications be covered by the appended claims.
, . .
Claims (59)
1. A method for applying electrically conductive printed patterns to insulating substrates wherein a metal-containing coating agent is transferred onto a substrate under the influence of energy radiation in a printed pattern to be produced and is chemically metallized, the coating agent includes a non-metallic grainy carrier substance having metal of the oxidation degree 0 applied thereto.
2. The method of Claim 1 wherein the carrier substance is constructed from a substance that has a structure that is fine-grained and surface-rich.
3. The method of Claim 1 wherein the carrier substance comprises grains having a size of less than approximately 8 microns.
4. The method of Claim 3 wherein the carrier substance comprises grains having a size greater than 1 micron.
5. The method of Claim 1 wherein the carrier substance comprises grains having a size of between approximately 2 microns to about 4 microns.
6. The method of Claim 1 wherein the carrier substance includes at least one compound chosen from the group consisting of: activated carbon, conductive lampblack, calcium carbonate, diatomaceous earth, bentonite, kaolin, silica gel, aluminum oxide, titinium oxide and pumice stone.
7. The method of Claim 1 wherein the carrier is constructed from activated carbon.
8. The method of Claim 1 wherein the carrier is constructed from calcium carbonate.
9. The method of Claim 1 wherein the carrier is constructed from a plastic.
10. The method of Claim 9 wherein the plastic is on an acrylate basis.
11. The method of Claim 1 wherein the carrier substance is constructed from the same material as the substrate.
12. The method of Claim 1 wherein the coating agent comprises approximately 0.01 to about 10 weight percent metal and approximately 90 to about 99.9 weight percent carrier substance.
13. The method of Claim 1 wherein the metal is chosen from the group consisting of the precious metals.
14. The method of Claim 13 wherein the metal is palladium.
15. The method of Claim 13 wherien the metal is platinum.
16. The method of Claim 1 wherein the metal is a precious metal alloy.
17. The method of Claim 16 wherein the metal is a precious metal alloy with a non-precious metal chosen from the group consisting of lead, zinc, nickel, tin, and copper.
18. The method of Claim 1 wherein the coating agent contains at least one bonding agent.
19. The method of Claim 18 wherein the coating agent includes at least one bonding agent chosen from the group consisting of polyamides, polyimides, colophonium resins, hydrocarbon resins, ketone resins, and polyvinylether.
20. The method of Claim 18 wherein the bonding agent includes at least one compound chosen from the group consisting of maleic resin and polyvinyl butyral.
21. The method of Claim 18 wherein the bonding agent is a hot-melt adhesive.
22. The method of Claim 18 wherein the carrier substance is saturated with the bonding agent.
23. The method of Claim 1 wherein the coating agent includes at least one solvent.
24. The method of Claim 23 wherein the coating agent includes at least one organic solvent.
25. The method of Claim 24 wherein the organic solvent is chosen from the group consisting of alcohols, esters, ketones, and hydrocarbons both aliphates and aromatics.
26. The method of Claim 23 wherein the coating agent includes at least one thixotroping agent.
27. The method of Claim 1 wherein the coating agent is applied to the substrate in a layer thickness of between approximately 4 microns to about 5 microns.
28. The method of Claim 23 wherein the coating agent is applied to the substrate by emersion.
29. The method of Claim 23 wherein printing ink is applied to the substrate by spraying.
30. The method of Claim 1 wherein the coating agent is anchored to the substrate by use of an energy beam deflectable in accord with a printed pattern to be generated.
31. The method of Claim 30 wherein a laser beam is employed as an energy beam.
32. The method of Claim 31 wherein the laser beam is generated with a CO2 laser.
33. The method of Claim 32 wherein the CO2 laser is operated with a mean power of between approximately 0.5 watts to about 8 watts.
34. The method of Claim 31 wherein the laser beam is generated with a Nd-YAG laser.
20a
20a
35. The method of Claim 34 wherein the Nd-YAG laser is operated with a mean power of between approximately 0.2 watts to about 50 watts.
36. The method of Claim 31 wherein the laser beam is focussed such that its diameter at the surface of the substrate lies between approximately 50 microns to about 400 microns.
37. The method of Claim 1 wherein after the transfer of a printed pattern excess coating agent is removed from the surface of the substrate.
38. The method of Claim 37 wherein the excess coating agent is removed with the assistance of a cleaning fluid.
39. The method of Claim 38 wherein an organic solvent is used as the cleaning fluid.
40. The method of Claim 38 wherein the excess coating agent is removed in an ultrasound bath.
41. The method of Claim 39 wherein isobutylmethylketone is used as the cleaning fluid.
42. The method of Claim 40 wherein after the removal of the excess coating agent, the anchoring of the printed pattern on the substrate is enhanced by applying heat to the printed pattern and substrate.
43. The method of Claim 42 wherein the heat is generated by microwaves.
44. The method of Claim 37 wherein after the removal of the excess coating agent, the anchoring of the printed pattern on the substrate is enhanced via a chemical after-treatment.
45. The method of Claim 44 wherein the chemical after-treatment is performed in an ammonia chloride bath.
46. The method of Claim 1 wherein a printed pattern transferred onto the substrate is completely built-up by chemical metal deposition.
47. The method of Claim 1 wherein a printed pattern transferred onto the substrate is built-up by chemical and subsequent galvanic metal deposition.
48. The method of Claim 46 wherein the printed pattern transferred onto the substrate is built-up by the deposition of copper.
49. The method of Claim 47 wherein the printed pattern transferred onto the substrata is built-up by the deposition of copper.
50. A metal-containing coating agent for applying electrically conductive printed patterns onto electrically insulating substrates comprising a non-metallic, grainy carrier to which is applied metal in the oxidation degree 0.
51. The metal-containing coating agent of Claim 59 wherein the coating agent includes a bonding agent.
52. The metal-containing coating agent of Claim 50 wherein the coating agent includes a solvent.
53. The metal-containing coating agent of Claim 50 wherein the coating agent includes a thixotroping agent.
54. The metal-containing coating agent of Claim 50 wherein the coating agent Includes palladium as the metal.
55. A metal-containing coating agent for applying electrically conductive printed patterns to electrically insulating substrates comprising:
a non-metallic, grainy carrier substance consisting of at least one compound chosen from the group consisting of:
activated carbon; conductive lampblack; calcium carbonate;
diatomaceous earth; bentonite; kaolin; silica gel; aluminum oxide; titinium oxide; plastic; and pumice stone; and a metal in the oxidation degree 0 that is applied to the carrier substance, the metal consisting of a compound chosen from the group consisting of: precious metals; precious metal alloys;
and precious metal alloys with non-precious metals chosen from the group consisting of zinc, nickel, tin, and copper.
a non-metallic, grainy carrier substance consisting of at least one compound chosen from the group consisting of:
activated carbon; conductive lampblack; calcium carbonate;
diatomaceous earth; bentonite; kaolin; silica gel; aluminum oxide; titinium oxide; plastic; and pumice stone; and a metal in the oxidation degree 0 that is applied to the carrier substance, the metal consisting of a compound chosen from the group consisting of: precious metals; precious metal alloys;
and precious metal alloys with non-precious metals chosen from the group consisting of zinc, nickel, tin, and copper.
56. The metal-containing coating agent of Claim 55 wherein the coating agent includes a bonding agent.
57. The metal-containing coating agent of Claim 55 wherein the coating agent includes a solvent.
58. The metal-containing coating agent of Claim 55 wherein the coating agent includes a thixotroping agent.
59. The metal-containing coating agent of Claim 55 wherein the coating agent includes palladium as the metal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3643130 | 1986-12-17 | ||
| DEP3643130.3 | 1986-12-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1325791C true CA1325791C (en) | 1994-01-04 |
Family
ID=6316414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 554456 Expired - Fee Related CA1325791C (en) | 1986-12-17 | 1987-12-16 | Method and coating material for applying electrically conductive printed patterns to insulating substrates |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4853252A (en) |
| EP (1) | EP0277325B1 (en) |
| JP (1) | JPS63166109A (en) |
| AT (1) | ATE63191T1 (en) |
| CA (1) | CA1325791C (en) |
| DE (1) | DE3769785D1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5114744A (en) * | 1989-08-21 | 1992-05-19 | Hewlett-Packard Company | Method for applying a conductive trace pattern to a substrate |
| DE4029522A1 (en) * | 1990-09-18 | 1992-03-19 | Bosch Gmbh Robert | METHOD FOR PRODUCING CONDUCTIVE STRUCTURES IN THICK LAYER TECHNOLOGY |
| US5153023A (en) * | 1990-12-03 | 1992-10-06 | Xerox Corporation | Process for catalysis of electroless metal plating on plastic |
| US5250758A (en) * | 1991-05-21 | 1993-10-05 | Elf Technologies, Inc. | Methods and systems of preparing extended length flexible harnesses |
| US5281447A (en) * | 1991-10-25 | 1994-01-25 | International Business Machines Corporation | Patterned deposition of metals via photochemical decomposition of metal-oxalate complexes |
| US5685939A (en) * | 1995-03-10 | 1997-11-11 | Minnesota Mining And Manufacturing Company | Process for making a Z-axis adhesive and establishing electrical interconnection therewith |
| DE19731346C2 (en) * | 1997-06-06 | 2003-09-25 | Lpkf Laser & Electronics Ag | Conductor structures and a method for their production |
| US5925402A (en) * | 1998-07-15 | 1999-07-20 | Morton International, Inc. | Method of forming a hidden identification using powder coating |
| FR2822167B1 (en) * | 2001-03-15 | 2004-07-16 | Nexans | METHOD FOR METALLIZING A SUBSTRATE PART |
| US6824857B2 (en) | 2001-04-02 | 2004-11-30 | Nashua Corporation | Circuit elements having an embedded conductive trace and methods of manufacture |
| US6717126B1 (en) | 2001-07-16 | 2004-04-06 | Amkor Technology, Inc. | Method of fabricating and using an image sensor package with reflector |
| US6686580B1 (en) | 2001-07-16 | 2004-02-03 | Amkor Technology, Inc. | Image sensor package with reflector |
| US7442408B2 (en) * | 2002-03-26 | 2008-10-28 | Hewlett-Packard Development Company, L.P. | Methods for ink-jet printing circuitry |
| EP1383364A3 (en) * | 2002-05-23 | 2006-01-04 | Nashua Corporation | Circuit elements having an ink receptive coating and a conductive trace and methods of manufacture |
| DE10237732B4 (en) * | 2002-08-17 | 2004-08-26 | BLZ Bayerisches Laserzentrum Gemeinnützige Forschungsgesellschaft mbH | Laser beam marking method and marking device for laser beam marking of a target substrate |
| JP2004311957A (en) * | 2003-03-26 | 2004-11-04 | Seiko Epson Corp | Device, its manufacturing method, electro-optical device, and electronic apparatus |
| JP4484578B2 (en) * | 2004-05-11 | 2010-06-16 | 株式会社リコー | Pattern shape body and method for manufacturing the same |
| US20050276933A1 (en) * | 2004-06-14 | 2005-12-15 | Ravi Prasad | Method to form a conductive structure |
| US20050274772A1 (en) * | 2004-06-14 | 2005-12-15 | Nelson Curtis L | Treating an area to increase affinity for a fluid |
| US20050274933A1 (en) | 2004-06-15 | 2005-12-15 | Peng Chen | Formulation for printing organometallic compounds to form conductive traces |
| US20050276911A1 (en) * | 2004-06-15 | 2005-12-15 | Qiong Chen | Printing of organometallic compounds to form conductive traces |
| US20060093732A1 (en) * | 2004-10-29 | 2006-05-04 | David Schut | Ink-jet printing of coupling agents for trace or circuit deposition templating |
| US7700911B1 (en) | 2005-03-04 | 2010-04-20 | University Of South Florida | Fabrication of 3-D ion optics assemblies by metallization of non-conductive substrates |
| FI20075474A0 (en) * | 2007-06-20 | 2007-06-20 | Valtion Teknillinen | Procedure for patterning a plastic surface |
| US8253233B2 (en) * | 2008-02-14 | 2012-08-28 | Infineon Technologies Ag | Module including a sintered joint bonding a semiconductor chip to a copper surface |
| US9435035B2 (en) | 2010-01-15 | 2016-09-06 | Byd Company Limited | Metalized plastic articles and methods thereof |
| CN102071424B (en) * | 2010-02-26 | 2012-05-09 | 比亚迪股份有限公司 | Plastic product and preparation method thereof |
| CN102071411B (en) | 2010-08-19 | 2012-05-30 | 比亚迪股份有限公司 | Plastic product and preparation method thereof |
| CN103813651B (en) * | 2013-11-07 | 2017-05-10 | 溧阳市江大技术转移中心有限公司 | CCL (Copper Clad Laminate) manufacturing method |
| CN103813642B (en) * | 2013-11-07 | 2017-02-01 | 溧阳市江大技术转移中心有限公司 | Method for forming conductive circuit on insulated metal substrate |
| US10247661B2 (en) * | 2016-07-20 | 2019-04-02 | Cook Medical Technologies Llc | Optical technique for coating characterization |
| CN116218205B (en) * | 2023-03-03 | 2024-03-29 | 金旸（厦门）新材料科技有限公司 | Electroplated heat-conducting nylon composite material and preparation method thereof |
Family Cites Families (7)
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|---|---|---|---|---|
| US3674515A (en) * | 1968-03-27 | 1972-07-04 | Du Pont | Metalizing composition including degassed platinum powders |
| US3787210A (en) * | 1971-09-30 | 1974-01-22 | Ncr | Laser recording technique using combustible blow-off |
| CA991332A (en) * | 1971-11-08 | 1976-06-15 | Owens-Illinois | Process for applying and bonding conductor material to substrate |
| WO1984003586A1 (en) * | 1983-03-02 | 1984-09-13 | Dennis R Mitchell | Method for bonding electrical conductors to an insulating substrate |
| US4486463A (en) * | 1983-12-21 | 1984-12-04 | Gte Laboratories, Incorporated | Selective metal plating onto poly(phenylene sulfide) substrates |
| US4574095A (en) * | 1984-11-19 | 1986-03-04 | International Business Machines Corporation | Selective deposition of copper |
| US4716059A (en) * | 1987-02-26 | 1987-12-29 | Allied Corporation | Composites of metal with carbon fluoride and method of preparation |
-
1987
- 1987-12-03 US US07/128,186 patent/US4853252A/en not_active Expired - Fee Related
- 1987-12-14 AT AT87118519T patent/ATE63191T1/en not_active IP Right Cessation
- 1987-12-14 JP JP62317255A patent/JPS63166109A/en active Pending
- 1987-12-14 DE DE8787118519T patent/DE3769785D1/en not_active Expired - Fee Related
- 1987-12-14 EP EP19870118519 patent/EP0277325B1/en not_active Expired - Lifetime
- 1987-12-16 CA CA 554456 patent/CA1325791C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ATE63191T1 (en) | 1991-05-15 |
| JPS63166109A (en) | 1988-07-09 |
| US4853252A (en) | 1989-08-01 |
| DE3769785D1 (en) | 1991-06-06 |
| EP0277325B1 (en) | 1991-05-02 |
| EP0277325A1 (en) | 1988-08-10 |
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