TWI445699B - A metal film forming method, and an article having a metal film - Google Patents
A metal film forming method, and an article having a metal film Download PDFInfo
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- TWI445699B TWI445699B TW100135711A TW100135711A TWI445699B TW I445699 B TWI445699 B TW I445699B TW 100135711 A TW100135711 A TW 100135711A TW 100135711 A TW100135711 A TW 100135711A TW I445699 B TWI445699 B TW I445699B
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- compound
- carbon atoms
- metal film
- hydrocarbon group
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- 239000002184 metal Substances 0.000 title claims description 132
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- 239000000758 substrate Substances 0.000 claims description 138
- 125000004432 carbon atom Chemical group C* 0.000 claims description 89
- 238000007747 plating Methods 0.000 claims description 85
- -1 chain Chemical group 0.000 claims description 73
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- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 47
- 125000003545 alkoxy group Chemical group 0.000 claims description 45
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 27
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- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 15
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 12
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- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229940098221 silver cyanide Drugs 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229920003194 trans-1,4-polybutadiene polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
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- 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
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
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- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- 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
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- 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
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- 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
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- 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
- C23C18/285—Sensitising or activating with tin based compound or composition
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- 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
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
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- 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
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/072—Electroless plating, e.g. finish plating or initial plating
-
- 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
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol
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- 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
- H05K2203/12—Using specific substances
- H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax or thiol
- H05K2203/124—Heterocyclic organic compounds, e.g. azole, furan
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
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- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Physics & Mathematics (AREA)
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Description
本發明係關於金屬膜形成方法以及具有金屬膜之製品。
鍍敷製品(例如,標誌等的汽車用裝飾鍍敷製品),有以ABS樹脂(高分子材料)組成基板之提案。在於此種鍍敷製品,重要的特性,係以鍍敷手段設於基板上的金屬膜(鍍敷膜)的密著性。密著力小,則金屬膜容易剝離。金屬膜的密著性大,則可增加製品的可靠度。
為了謀求上述密著性的提升,有於基板表面上形成微細凹凸的提案。即,提案基板表面的粗化。藉此,可期待所謂錨定效果(咬入效果),而提升密著力。
為使基板表面粗化,已知例如以氧化劑(例如,過錳酸鹽、六價鉻酸等的水溶液)蝕刻。然而,可採用藉由六價鉻酸的蝕刻技術的只有樹脂係如ABS樹脂之具有不飽和基的樹脂之情形。因此,基板材料有所限制。再者,六價鉻酸的使用,近幾年,限制提高。因此,正在探索可取代六價鉻酸的物質。但是,仍無有效的對策。
電路基板,隨著技術的進步,被要求高積體化或高密度化。由此,關於電路基板,於基板的銅箔表面所存在的凹凸越少越好。但是,設於被蝕刻之基板表面之金屬膜(例如,Cu膜)具有凹凸。金屬膜(Cu膜)具有凹凸,則流通金屬膜之訊號傳輸距離會變長。傳輸損耗(訊號衰減)亦變大。再者,會發熱。因此,金屬膜(Cu膜)凹凸度越小越好。即,表面粗糙度小的基板被期望。
為應付Cu的資源問題或配線圖案的微細化的進行,在於電路基板的配線電路的構築,開始被採用半加成法。由如此之觀點,亦期望表面粗糙小的基板。
為提高基板與金屬膜的密著性,已知有電暈放電處理(或電漿放電處理)。藉由此種處理,於基板表面導入OH基。藉由該OH基的存在,可提升設於其上之鍍敷膜之密著性。
但是,電暈放電處理(或電漿放電處理)有使基板惡化之虞。並且,雖說會生成OH基,但其數目並不多。由此,密著力的提升有限。再者,電暈放電處理(或電漿放電處理),在被處理物的形狀或大小有所限制。並且,放電處理之工作性並不佳。
專利文獻
專利文獻1:日本特開2006-213677號公報
專利文獻2:日本特開2007-17921號公報
專利文獻3:日本特開2007-119752號公報
非專利文獻
非專利文獻1:日本接著學會誌「21世紀的接著技術」森邦夫vol.43(6) 242-248(2007)
非專利文獻2:表面技術誌「無六價鉻樹脂鍍敷」森邦夫阿部四郎vol.59(5) 299-304(2008)
本發明者,在以濕式鍍敷手段於聚合物製基板上設置金屬膜時,認為金屬膜之密著現象係接著現象之一。而認為只要於上述基板上設置使聚合物製基板與金屬膜的雙方結合之劑(例如,由本發明者所提倡,稱為分子接合劑之劑),即可提升金屬膜的密著性。
然而,即使使用稱為分子接合劑之化合物,並未能滿足設於聚合物製基板上設置之金屬鍍敷膜的密著強度。因為過去的分子接合劑,係於基板表面施以電暈放電處理(或電漿放電處理)為前提。
因此,本發明所欲解決的課題,係即使無須採用酸(例如,六價鉻酸等)之蝕刻、電暈放電處理(或電漿放電處理),即可提高所形成之金屬膜之密著力之技術。
上述課題,可藉由一種金屬膜形成方法解決:該金屬膜之形成方法,包含:於基體表面設置包含下述化合物(α)之劑之步驟(X);及於上述化合物(α)的表面,藉由濕式鍍敷的手法,設置金屬膜的步驟(Y),其特徵在於:上述化合物(α)係於一分子內,具有OH基或OH生成基、及疊氮基、與三嗪環之化合物,上述基體係使用聚合物構成而成。
較佳的是於上述金屬膜形成方法,進一步具備:於上述步驟(X)之後,且在於上述步驟(Y)之前,對存在於上述基體表面之上述化合物(α)照射既定圖案的光的步驟(W)為特徵之金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,藉由上述步驟(W)的光照射,使上述基體與上述化合物(α)的疊氮基進行化學反應,使上述化合物(α)與上述基體表面鍵結為特徵之金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,上述光係紫外線為特徵之金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,上述OH基或OH生成基,係烷氧基矽基(亦包含上述烷氧基為OH基之情形。)為特徵之金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,上述化合物(α)係以下述通式[I]所示的化合物為特徵的金屬膜形成方法解
決。
較佳的是於上述金屬膜形成方法,上述化合物(α)係以下述通式[Io]所示的化合物為特徵的金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,上述化合物(α)係以下述通式[Ia]所示的化合物為特徵的金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,上述化合物(α)係以下述通式[Ib]所示的化合物為特徵的金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,進一步於上述步驟(X)之後,且於上述步驟(Y)之前,於上述化合物(α)的表面,設置以下述通式[II]所示之物質之步驟(V)為特徵的金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,進一步於上述步驟(x)或步驟(V)之後,且於上述步驟(Y)之前,於上述化合物(α)的表面,設置烷氧基矽基、烷氧基鋁基及/或烷氧基鈦基的化合物(β)之步驟(U)為特徵的金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,上述化合物(β)係以下述通式[T]所示的化合物為特徵的金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,上述化合物(β)係以下述通式[III]所示的化合物為特徵的金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,上述化合物(β)係以下述通式[IV]所示的化合物為特徵的金屬膜形成方法解決。
較佳的是於上述金屬膜形成方法,上述基體係配線用基板,金屬膜的一部分係至少包含Cu之鍍敷膜為特徵的金屬膜形成方法解決。
上述課題,可以一種具有金屬膜之製品解決:該具有金屬膜之製品,包含:基體;設置於上述基體表面之下述化合物(α);及設於上述化合物(α)上之濕式鍍敷金屬膜而成,其特徵在於:上述化合物(α)係於一分子內,具有OH基或OH生成基、及疊氮基、與三嗪環之化合物,上述基體係使用聚合物構成而成。
較佳的是於上述製品,上述基體與上述化合物(α)係化學鍵結而成為特徵的金屬膜的製品解決。
較佳的是於上述製品,上述OH基或OH生成基係烷氧基矽基(亦包含上述烷氧基為OH基之情形。)為特徵的具有金屬膜的製品解決。
較佳的是於上述製品,上述化合物(α)係以下述通式[I]所示的化合物為特徵的具有金屬膜之製品解決。
較佳的是於上述製品,上述化合物(α)係以下述通式[Io]所示的化合物為特徵的具有金屬膜之製品解決。
較佳的是於上述製品,上述化合物(α)係以下述通式[Ia]所示的化合物為特徵的具有金屬膜之製品解決。
較佳的是於上述製品,上述化合物(α)係以下述通式[Ib]所示的化合物為特徵的具有金屬膜之製品解決。
較佳的是於上述製品,上述化合物(α)係以下述通式[II]所示的化合物為特徵的具有金屬膜之製品解決。
較佳的是於上述製品,將具有烷氧基矽基、烷氧基鋁基及/或烷氧基鈦基的化合物(β),設於上述化合物(α)的表面為特徵的具有金屬膜之製品解決。
較佳的是於上述製品,上述化合物(β)係以下述通式[T]所示的化合物為特徵的具有金屬膜之製品解決。
較佳的是於上述製品,上述化合物(β)係以下述通式[III]所示的化合物為特徵的具有金屬膜之製品解決。
較佳的是於上述製品,上述化合物(β)係以下述通式[IV]所示的化合物為特徵的具有金屬膜之製品解決。
較佳的是上述製品係配線基板為特徵的具有金屬膜之製品解決。
式中,E係任意之基體。F係OH基或OH生成基。-Q係-N3
又-NR1
(R2
)。-NR1
(R2
)的R1
、R2
係H、碳數1~24之烴基、或-RSi(R’)n
(OA)3-n
(R係碳數1~12之鏈狀的烴基。R’係碳數1~4之鏈狀的烴基。A係,H或碳數1~4鏈狀的烴基。n是0~2的整數。)。R1
與R2
,可為相同亦可不同。
通式[Io]
式中-Q係-N3
或-NR1
(R2
)。R1
、R2
係H、碳數1~24之烴基或-RSi(R’)n
(OA)3-n
(R係碳數為1~12之鏈狀的烴基。R’係碳數為1~4之鏈狀的烴基。A係,H或碳數1~4之鏈狀的烴基。n係0~2之整數。)。在於R1
、R2
之至少一個係上述-RSi(R’)n
(OA)3-n
。R1
與R2
,可為相同亦可不同。
通式[Ia]
式中R1
、R2
係H、碳數1~24之烴基或-RSi(R’)n
(OA)3-n
(R係碳數為1~12之鏈狀的烴基。R’係碳數為1~4之鏈狀的烴基。A係,H或碳數1~4之鏈狀的烴基。n係0~2之整數。)。在於R1
、R2
之至少一個係上述-RSi(R’)n
(OA)3-n
。R1
與R2
,可為相同亦可不同。
通式[1b]
式中R1
、R2
係H、碳數1~24之烴基或-RSi(R’)n
(OA)3-n
(R係碳數為1~12之鏈狀的烴基。R’係碳數為1~4之鏈狀的烴基。A係,H或碳數1~4之鏈狀的烴基。n係0~2之整數。)。在於R1
、R2
之至少一個係上述-RSi(R’)n
(OA)3-n
。R1
與R2
,可為相同亦可不同。
通式[II]
式中X’、Y’係Si或Ti。Z係Al。G係,碳數1~3之烴基或碳數1~3之烷氧基。B係碳數1~3之烷氧基。n、m係0~200之整數(其中,2≦n+m≦400)。p係0~100之整數。
通式[T]
L-Si(M’)n
(OM)3-n
式中,L係有機基(有機基亦可包含碳、氫以外的元素。有機基亦可包含取代基。有機基可為脂肪族、芳香族、鏈狀、環類之任何形態。)。M’係碳數1~4之鏈狀烴基。M係H或碳數1~4之鏈狀烴基。n係0~2之整數。上述M’與M可相同亦可不同。
通式[III]
式中,R5
係碳數1~12之烴基。R6
係H或碳數1~10之烴基。X"係H或碳數1~10之烴基。Y"係碳數1~10之烷基氧基。n係1~3之整數。M1
係H、Li、Na、K或Cs。
通式[IV]
式中,R5
係碳數1~12之烴基。R7
係碳數1~12之烴基。X"係H或碳數1~10之烴基。Y"係碳數1~10烷基氧基。所有的X"及Y"可為相同亦可不同。n、m係1~3之整數。M1
係H、Li、Na、K或Cs。
可形成密著性高的金屬膜。可得例如,金屬鍍敷膜不容易剝離的製品(例如,功能性製品(電路基板)或創意(裝飾)製品)。
第1本發明係金屬膜形成方法。特別是藉由濕式鍍敷的手法,形成金屬膜時所使用的方法。例如,配線基板等之功能性基板之製造方法。或,創意製品(裝飾製品)的製造方法。本方法,具備:步驟(X)及步驟(Y)。上述步驟(X)係於基體表面,設置包含化合物(α)之劑的步驟。上述步驟(Y)係於上述化合物(α)的表面上,藉由濕式鍍敷的手法,設置金屬膜之步驟。上述化合物(α)係於一分子內,具有OH基或OH生成基、及疊氮基。上述基體係使用聚合物所構成而成。
上述步驟(X)係於包含上述化合物(α)(例如溶解或分散)之溶液中,浸泡基體而達成。亦可藉由將上述溶液,噴附在基體之所需之處(全面或部分)而達成。之後,亦可按照需要,進行乾燥。即,藉由溶劑的揮散,上述化合物(α)殘留於基體表面。
上述方法,特別是進一步具備光照射步驟為佳。即,光對存在於上述基體表面的上述化合物(α)照射。結果,上述基體與上述化合物(α)的疊氮基進行化學反應。然後,上述化合物(α)鍵結於上述基體表面。在沒有光照射之處,難以促進化學反應。因此,之後清洗,則只有在光照射的部位,成上述化合物(α)存在(鍵結)於上述基體表面者。為使光不會照射到特定處,只要在光照射(曝光)時,於特定處配置光罩即可。於光照射時,可使用反射板或反射膜。藉此,可提高照射效率。擴大照射範圍。上述光,以紫外線為佳。
上述化合物(α)之OH基或OH生成基,以烷氧基矽基(亦包含上述烷氧基為OH基之情形。)為佳。此時,上述化合物(α)具有烷氧基矽基與疊氮基。進一步具有三嗪環為佳。
上述化合物(α),以於三嗪(其中,以1,3,5-三嗪),至少與一個疊氮基及至少一個烷氧基矽基,直接或間接地鍵結的構造。
上述化合物(α)以上述通式[I]所示的化合物為佳。以上述通式[Io]所示的化合物更佳。
進一步以上述通式[Ia]或[Ib]所示的化合物為佳。
上述通式中,-Q係-N3
或-NR1
(R2
)。R1
、R2
係H、碳數1~24之烴基或-RSi(R’)n
(OA)3-n
(R係碳數為1~12之鏈狀的烴基。R’係碳數為1~4之鏈狀的烴基。A係,H或碳數1~4之鏈狀的烴基。n係0~2之整數。)。R1
與R2
,可為相同亦可不同。
上述通式[Ia]中,R1
、R2
係H、碳數1~24之烴基或-RSi(R’)n
(OA)3-n
。上述碳數1~24之烴基係鏈狀的烴基、具有取代基(環狀或鏈狀)之鏈狀的烴基、環狀基、或具有取代基(環狀或鏈狀)之環狀基。例如-Cn
H2n+1
、-Cn
H2n-1
、-C6
H5
、-CH2
CH2
C6
H5
、-CH2
C6
H5
、-C10
H7
等。上述-RSi(R’)n
(OA)3-n
的R係碳數為1~12之鏈狀的烴基(例如,-Cn
H2n
)。上述R’係碳數1~4之鏈狀的烴基(例如,-Cn
H2n+1
)。上述A係,H或碳數1~4鏈狀的烴基(例如-CH3
、-C2
H5
、-CH(CH3
)2
、-CH2
CH(CH3
)2
、-C(CH3
)3
)。n係0~2之整數。在於R1
、R2
之至少一個係上述-RSi(R’)n
(OA)3-n
。R1
與R2
,可為相同亦可不同。於本說明書所謂具有取代基之基(例如,烴基)係指例如上述基(例如,烴基)之H被可取代之適宜官能基取代者。
上述通式[Ib]中、R1
、R2
係H、碳數1~24之烴基或-RSi(R’)n
(OA)3-n
。上述碳數1~24之烴基係鏈狀的烴基、具有取代基(環狀或鏈狀)之鏈狀的烴基、環狀基、或具有取代基(環狀或鏈狀)之環狀基。例如-Cn
H2n+1
、-Cn
H2n-1
、-C6
H5
、-CH2
CH2
C6
H5
、-CH2
C6
H5
、-C10
H7
等。上述-RSi(R’)n
(OA)3-n
的R係碳數為1~12之鏈狀的烴基(例如,-Cn
H2n
)。上述R’係碳數1~4之鏈狀的烴基(例如,-Cn
H2n+1
)。上述A係,H或碳數1~4鏈狀的烴基(例如-CH3
、-C2
H5
、-CH(CH3
)2
、-CH2
CH(CH3
)2
、-C(CH3
)3
)。n係0~2之整數。在於R1
、R2
之至少一個係上述-RSi(R’)n
(OA)3-n
。R1
與R2
,可為相同亦可不同。
上述方法較佳的是進一步於上述步驟(X)之後,且於上述步驟(Y)之前,於上述化合物(α)的表面,設置以下述通式[II]所示之物質之步驟(V)。即,藉由於表面存在上述通式[II]所示的聚合物,使存在於表面的-OH基數量增加,而改善金屬膜的密著性(耐剝離性)。
上述通式[II]中,X’、Y’係Si或Ti。Z係Al。G係,碳數1~3之烴基(例如-CH3
、-C2
H5
、-CH=CH2
)、或碳數1~3之烷氧基(例如,-OCH3
、-OC2
H5
)。B係碳數1~3之烷氧基(例如,-OCH3
、-OC2
H5
)。n、m係0~200之整數(其中,2≦n+m≦400)。p係0~100之整數。以n≠1、m≠1、p≠1為佳。
上述方法較佳的是進一步於上述步驟(X)(或步驟(V))之後,且於上述步驟(Y)之前,於上述化合物(α)的表面,設置烷氧基矽基、烷氧基鋁基及/或烷氧基鈦基的化合物(β)之步驟(U)。即,藉由於表面存在上述化合物(β),使存在於表面的-OH基數量增加。或者,進一步,導入反應性官能基。然後,改善金屬膜的密著性(耐剝離性)。在此,上述化合物(β),以上述通式[T][III]或[IV]所示的化合物為佳。
上述通式[III][IV]中,R5
、R7
係碳數1~12之烴基。R6
係H或碳數1~10之烴基。上述烴基係鏈狀的烴基或環狀的烴基。更具體而言,係飽和脂肪烴基。或者,係不飽和脂肪烴基。或係芳香烴基。上述脂肪烴基,可為直鏈烴基,亦可為具有分枝鏈的烴基。上述芳香烴基、有具有取代基之情形,與不具有取代基之情形。再者,上述R5
、R7
有具有-NH-、-CO-、-O-、-S-、-COO-等之情形,及不具有之情形。X"係,H或碳數是1~10烴基。該烴基係鏈狀的烴基。更具體而言,係飽和脂肪烴基。或者,係不飽和脂肪烴基。該等的脂肪烴基,雖不具有環狀基,惟亦有具有環狀基作為取代基之情形。Y",碳數1~10之烷基氧基。n係1~3之整數。M1
係H、Li、Na、K或Cs。
於金屬薄膜之形成,有以乾式鍍敷(蒸鍍或濺鍍)之手法及以濕式鍍敷之手法。於上述步驟(Y),採用濕式鍍敷之手法。上述濕式鍍敷係例如無電電鍍。或者,電鍍。可僅採用任意一方,亦可採用兩者。此外,本技術可採用習知之技術。
本發明之第2係具有金屬膜之製品。例如,功能性鍍敷製品(運輸機器(例如,汽車),或者在於電器‧電子機器之配線基板(印刷配線基板、電路基板)。創意製品(裝飾製品)。所謂本製品係指具備:基體;設於上述基體表面之化合物(α);及設於上述化合物(α)上之濕式鍍敷金屬膜。上述化合物(α)係於一分子內,具有OH基或OH生成基、疊氮基。化合物(α)係上述之化合物。按照需要,可與上述化合物(α)一起使用上述通式[II][T][111]或[IV]所示之化合物。上述基體係使用聚合物構成而成。
在於本發明,於基體的表面,可使例如以通式[I][Io][Ia]或[Ib]所示化合物(α),與增感劑(例如通式[II][T][III]或[IV]所示的化合物)共存。然後,之後,做光(紫外線)照射。或於加熱之後做光照射。於本發明,於基體的表面,設置上述通式[I][Io][Ia]或[Ib]所示化合物(α)。或,進一步設置增感劑(例如通式[II][T][III]或[IV]所示的化合物)。然後,進行光照射。或,加熱之後做光照射。之後,浸漬於酸性溶液中或鹼性溶液中為佳。
在於本發明,亦可與上述增感劑一起,或取代上述增感劑,使用具有烷氧基矽基之矽烷偶合劑或二苯甲酮系等的光增感劑。
根據上述發明,藉由化合物(α)的疊氮基與基體的化學反應(鍵結),例如於基體表面導入烷氧基矽基。然後,使烷氧基矽基變性而生成OH基。結果,提升以濕式鍍敷所設置之金屬薄膜(鍍敷膜)的密著性(耐剝離性)。先前,為提升金屬薄膜(鍍敷膜)的密著性(耐剝離性),進行基體表面的粗化。即,對基體進行以六價鉻酸或硫酸等的強酸處理,但已無需該處理。再者,先前於進行分子接合劑處理之前所實施之電暈放電處理或電漿處理,則有使樹脂製的基體惡化之虞。但是,已無需該等處理。
於基體表面設置上述化合物(α)。之後做光照射。此時,將於上述化合物(α)與基體的之間發生化學反應。結果,上述化合物(α)會與基體鍵結。基體係以聚合物構成。上述聚合物,可舉硬化性樹脂(例如熱硬化性樹脂、光硬化性樹脂、電子線硬化性樹脂)或熱塑性樹脂。亦可舉纖維強化樹脂。亦可舉橡膠(加硫橡膠)。在其他,以於表面上設置包含聚合物之塗膜者亦可。
疊氮化合物已知係架橋劑。對包含疊氮化合物的組合物進行紫外線照射,則可得架橋構造之聚合物。但是,在於聚合物表面存在疊氮化合物的狀況下,並不知道疊氮是否會與聚合物(聚合物表面的分子鏈)做化學鍵結。
由本發明者嘗試如下實驗。於聚合物表面,設置上述化合物(α)(特別是以通式[I][Io][Ia][1b]所示的化合物)。之後做光照射。結果於疊氮基與聚合物(聚合物表面的分子鏈)之間發生化學反應。即,於上述化合物(α)與上述聚合物的之間產生化學鍵結。然後,發現烷氧基矽基存在於聚合物表面。此係並無法由先前的知識想像者。然後,以烷氧基矽基表面改質之基體,以上述通式[I][III][IV]所示化合物或矽烷偶合劑處理。藉此,更加提升金屬膜的密著性。
以下,由與上述不同的觀點說明本發明。
[化合物α(密著性提昇劑:分子接合劑)]
本發明的密著性提升劑(化合物(α)),亦可說是分子接著劑。
上述化合物(α)具有烷氧基矽基及疊氮基。進一步具有三嗪環為佳。疊氮基直接與三嗪環(C原子)鍵結為佳。鍵結於三嗪環之疊氮基之數,例如為一個或兩個。OH基或OH生成基(例如,烷氧基矽基),以間接地經由間隔基(例如,胺基、氧基及/或烴基)與三嗪環(C原子)鍵結。間接地鍵結之烷氧基矽基為一個或兩個以上。
發現與三嗪環(共軛系骨架)鍵結之疊氮基,氮烯的分解能很高。因此,不容易受到近紫外線、可視光的影響。因此,可改善紫外線曝光的工作性。亦發現與三嗪環鍵結的氮烯,與並非如此之氮烯相比,較安定。亦發現可抑制氮烯相互的鍵結。亦發現可增強對C-H鍵結之拔氫活性或對不飽和鍵結之加成活性。
上述烷氧基矽基,對三嗪環(共軛系骨架),經由間隔基(例如胺基、羥基及/或烴基)鍵結。因此,上述化合物(α)鍵結於聚合物表面時,在於與金屬膜的接觸,生成化學鍵結的熵效果會提升。熵效果的提升,於聚合物(上述基體)與金屬膜(鍍敷膜)接觸之後,可增大在於界面反應之頻率因子項。結果,會增加界面反應的機會。上述間隔基的長度,會反映在界面反應的頻率因子的增大。間隔基過長,則成本會變高。且,會發生分子接合劑的吸附量的減少。因此,以適當長度的間隔基為佳。由如此之觀點,以上述通式[Io][Ia][1b]所示的化合物為佳。
由在於界面反應之頻率因子項的增大的觀點,存在於1分子中的烷氧基矽基與疊氮基數量多為佳。但是,由成本等的觀點,此數量亦有所限制。即,以上述通式[Io][Ia][1b]所示的化合物為佳。
在於上述通式[Io][Ia][1b]的烷氧基矽基,多數情形係OH生成基(OH的前驅物)。為將OH生成基變性為OH基,例如以水(中性水、酸性水、鹼性水)處理。其他,亦可考慮電暈放電處理及電漿處理。但是,以水處理為佳。
化合物(α)係沿著下述反應式合成。
包含羥基之胺基化合物(例如,胺基醇)之丙酮溶液,於攪拌下,滴入三聚氰氯之丙酮溶液。此時的溫度為0~10℃。之後,滴入NaOH水溶液。藉此,得到RDC。對該RDC之二甲基甲醯胺(DMF)溶液,滴入NaN3
的DMF溶液。此時的溫度為40~60℃。藉此,得到DAZ。亦可取代上述丙酮,使用醇(例如甲醇、乙醇等)。
包含羥基之胺基化合物(例如,烷氧基矽基烷基胺)之THF(四氫呋喃)溶液,於攪拌下,滴入三聚氰氯之THF溶液。此時之溫度為0~50℃。之後,滴入NaOH水溶液。藉此得到RMC。對該RMC的DMF溶液,滴入NaN3
的DMF溶液。此時的溫度為50~70℃。藉此,得到MAZ。亦可取代上述丙酮,使用醇(例如甲醇、乙醇等)。
NaN3
水溶液,於攪拌下,三聚氰氯之丙酮溶液。此時的溫度為0~5℃。藉此,得到ADC。對該ADC的丙酮溶液,滴入包含羥基之胺基化合物(例如,胺基醇)溶液。此時的溫度為40~60℃。藉此,得到MAZ。亦可取代上述丙酮,使用醇(例如甲醇、乙醇等)。
NaN3
水溶液,於攪拌下,三聚氰氯之丙酮溶液。此時的溫度為0~10℃。藉此,得到AMC。對AMC的丙酮溶液,滴入包含羥基之胺基化合物(例如,胺基醇)溶液。此時的溫度為0~60℃。藉此,得到DAZ。亦可取代上述丙酮,使用醇(例如甲醇、乙醇等)。
上述化合物(α)係具有烷氧基矽基及疊氮基的三嗪系的化合物。如此之化合物較佳的是上述通式[I][Io][Ia][1b]所示的化合物。該等化合物,可舉例如6-疊氮-2,4-雙(乙醇胺基)-1,3,5-三嗪、6-疊氮-2,4-雙(己醇胺基)-1,3,5-三嗪、6-疊氮-2,4-雙(癸醇胺基)-1,3,5-三嗪、6-疊氮-2,4-雙(3,4-二羥基苯基)胺基)-1,3,5-三嗪、6-疊氮-2,4-雙(2,2-二羥甲基)乙基胺基-1,3,5-三嗪、6-疊氮-2,4-雙(三甲醇甲基)甲基胺基-1,3,5-三嗪、6-疊氮-2,4-(1,2-二羥丙基)胺基-1,3,5-三嗪、6-疊氮-2,4-雙(3-乙氧基矽基)丙基胺基-1,3,5-三嗪(TE-MAZ)、6-疊氮-2,4-雙(3-甲基乙基酮氧基矽基)丙基胺基-1,3,5-三嗪、6-疊氮-2,4-雙(3-三異丙氧基矽基)丙基胺基-1,3,5-三嗪、6-疊氮-2,4-雙(3-三乙醯氧基矽基)丙基胺基-1,3,5-三嗪、6-疊氮-2,4-雙(3-三異丙烯氧基矽基)丙基胺基-1,3,5-三嗪、6-疊氮-2,4-雙(3-三異丙氧基矽基)丙基胺基-1,3,5-三嗪、6-疊氮-2,4-雙(3-苯甲醯氧矽基)丙基胺基-1,3,5-三嗪、6-疊氮-2,4-雙(二乙醇胺基)-1,3,5-三嗪、6-疊氮-2,4-雙(二己醇胺基)-1,3,5-三嗪、6-疊氮-2,4-雙(二癸醇胺基)-1,3,5-三嗪、6-疊氮-2,4-(3-三乙氧基矽基丙基)胺基-1,3,5-三嗪、6-疊氮-2,4-雙(6-三乙氧基矽基己基)胺基-1,3,5-三嗪、6-疊氮-2,4-雙(10-三乙氧基矽基十二基)胺基-1,3,5-三嗪、2,4-二疊氮-6-(N,N-二乙醇)胺基-1,3,5-三嗪(DEA-DAZ)、2,4-二疊氮-6-(N,N-二癸醇)胺基-1,3,5-三嗪、2,4-二疊氮-6-(3,4-二羥基苯基)胺基)-1,3,5-三嗪、2,4-二疊氮-6-(2,2-二羥甲基)乙基胺基-1,3,5-三嗪、2,4-二疊氮-6-(三甲醇甲基)甲基胺基-1,3,5-三嗪、2,4-二疊氮-6-(1,2-二羥基丙基)胺基-1,3,5-三嗪、2,4-二疊氮-6-(3-三乙氧基矽基丙基)胺基-1,3,5-三嗪(TE-DAZ)、2,4-二疊氮-6-雙(3-甲基乙基酮肟基矽基)丙基胺基-1,3,5-三嗪、2,4-二疊氮-6-雙(3-甲基乙基酮肟基矽基)丙基胺基-1,3,5-三嗪、2,4-二疊氮-6-(3-三異丙氧基矽基)丙基胺基-1,3,5-三嗪、2,4-二疊氮-6-(3-三乙醯氧基矽基)丙基胺基-1,3,5-三嗪、2,4-二疊氮-6-(3-三異丙烯氧基矽基)丙基胺基-1,3,5-三嗪、2,4-二疊氮-6-(3-三異丙氧基矽基)丙基胺基-1,3,5-三嗪、2,4-二疊氮-6-(3-三苯甲醯氧矽基)丙基胺基-1,3,5-三嗪、2,4-二疊氮-6-雙(二羥基乙基)胺基-1,3,5-三嗪、2,4-二疊氮-6-(N,N-二己醇)胺基-1,3,5-三嗪、2,4-二疊氮-6-(N,N-二癸醇)胺基-1,3,5-三嗪、2,4-二疊氮-6-(N,N-雙(3-三乙氧基矽基丙基)胺基-1,3,5-三嗪(BTE-DAZ)、2,4-二疊氮-6-(N,N-雙(6-三乙氧基矽基己基)胺基-1,3,5-三嗪、6-(11-三乙氧基矽基十一基)胺基-1,3,5-三嗪-2,4-二疊氮(TEU-DAZ)、6-(3-二乙氧甲基矽基丙基)胺基-1,3,5-三嗪-2,4-二疊氮(DEM-DAZ)、6-(4-三嗪、乙氧基矽基丁基)胺基-1,3,5-三嗪-2,4-二疊氮(TEB-DAZ)等。
[基體(聚合物)]
基體係以聚合物(樹脂)構成。上述聚合物,具有例如C-H鍵結或Si-C鍵結。特別是,具有C-H鍵結。上述聚合物係硬化性樹脂(例如熱硬化性樹脂、光硬化性樹脂、電子線硬化性樹脂)。或係熱塑性樹脂。或係纖維強化樹脂。或係加硫橡膠或未加硫橡膠。其他,以於表面上設置包含聚合物之塗膜者亦可。上述聚合物係二維線狀構造。或係三維網眼構造。基體的形狀係根據用途決定。例如薄膜狀、薄片狀、板狀、柱狀、棒狀、框狀、箱狀、纖維狀、絲狀、布狀、不織布狀、發泡體狀等的形狀。
上述聚合物等的具體例,可舉例如纖維素及其衍生物、羥基乙基纖維素、澱粉、二醋酸纖維素、表面皂化醋酸乙烯酯樹脂、低密度聚乙烯、高密度聚乙烯、聚丙烯。乙烯丙烯共聚物、石油樹脂、聚苯乙烯、間同立構-聚苯乙烯、苯乙烯共聚物、香豆酮-茚樹脂、松烯樹脂、苯乙烯-二乙烯基苯共聚物、丙烯腈-丁二烯-苯乙烯共聚樹脂、聚丙烯酸甲酯、聚丙烯酸乙酯、聚丙烯腈、聚丙烯酸甲酯、聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯、聚胺基丙烯酸酯、聚醋酸乙烯醋、乙烯-醋酸乙烯酯共聚樹脂、聚乙烯醇、聚乙烯醇縮甲醛、聚乙烯醇縮醛、醋酸乙烯酯共聚物、聚氯乙烯、氯乙烯-醋酸乙烯酯共聚物、氯乙烯-乙烯共聚物、聚偏氟乙烯、偏氟乙烯-乙烯共聚物、偏氟乙烯-丙烯共聚物、反式-1,4-聚丁二烯、反式-1,2-聚丁二烯、聚甲醛、聚乙二醇、聚丙二醇、酚-甲醛樹脂、甲酚-甲醛樹脂、間苯二酚樹脂、三聚氰胺樹脂、二甲苯樹脂、甲苯樹脂、醇酸樹脂、變性醇酸樹脂、聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、不飽和聚酯樹脂、聚酯丙烯酸酯、烯丙酯樹脂、聚碳酸酯、6-尼龍、6’,6-尼龍、6’,10-尼龍、聚醯亞胺、聚醯胺、聚苯並咪唑、聚苯並噁唑、聚苯並噻唑、聚醯亞胺醯胺、矽樹脂、加成硬化型矽酮橡膠、聚合硬化型矽酮橡膠、縮合硬化型矽酮橡膠、加成硬化型矽酮樹脂、呋喃樹脂、聚氨脂樹脂、環氧樹脂、聚苯醚樹脂、聚二甲基苯醚、聚苯醚或聚二甲基苯醚與三聚異氰尿酸三烯丙酯之混合聚合物(聚合物合金)、聚苯醚或聚二甲基苯醚與過氧化三聚異氰尿酸三烯丙酯之混合聚合物(聚合物合金)、聚二甲苯、聚苯硫醚、聚環烯烴、聚碸、聚醚碸、聚醚醚酮、聚亞醯胺、液晶樹脂(LCP)、天然橡膠、順式-1,4-丁二烯橡膠、異戊二烯橡膠、聚氯丁烯、苯乙烯-丁二烯共聚橡膠、加氫苯乙烯-丁二烯共聚橡膠、丙烯腈-丁二烯共聚橡膠、加氫丙烯-丁二烯共聚橡膠、聚丁烯橡膠、聚異丁烯橡膠、乙烯-丙烯橡膠、乙烯-丙烯-二烯橡膠、環氧乙烷-環氧氯丙烷共聚橡膠、氯化聚乙烯橡膠、氯硫化聚乙烯橡膠、烷基化氯硫化聚乙烯橡膠、氯丁二烯橡膠、氯化丙烯酸橡膠、溴化丙烯酸橡膠、氟橡膠、環氧氯丙烷共聚橡膠、氯化乙烯-丙烯橡膠、氯化異丁烯橡膠、溴化異丁烯橡膠、四氟乙烯、六氟丙烯、偏氟乙烯及四氟乙烯等的單獨聚合物橡膠及該等的二元以及三元共聚物橡膠、乙烯-四氟乙烯共聚橡膠、丙烯-四氟乙烯共聚橡膠、乙烯丙烯酸橡膠、過氧化物型矽酮橡膠、加成型矽酮橡膠、縮合型矽酮橡膠、環氧橡膠、聚氨酯橡膠、兩末端不飽和基彈性體等。
上述基體(聚合物),按照需要,包含各種添加劑(例如架橋劑、架橋促進劑、架橋助劑、自由基起始劑、陽離子起始劑、光聚合起始劑、焦化防止劑、安定劑、老化防止劑、紫外線防止劑、填充劑、增強劑、可塑劑、軟化劑、著色劑、黏度調整劑等)。
上述三維網眼構造聚合物,係例如對上述二維線狀聚合物添加架橋劑(進一步,架橋促進劑或架橋助劑)的組合物,進行加熱或光照射而得。或者,將既定的單體(例如乙烯基、丙烯酸酯基、甲基丙烯酸酯基、環氧基、異氰酸酯基、或氧雜環丁烷基,於一分子中具有1個或2個之低分子單體)添加架橋劑(進一步,架橋促進劑或架橋助劑)的組合物,進行加熱或光照射而得。
上述單體,可舉例如氨酯丙烯酸酯系、環氧丙烯酸酯系、酯丙烯酸酯系、丙烯酸酯系、環氧系、乙烯基醚系的單體。具體而言,丙烯酸酯類(例如乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己烷二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、異戊四醇四(甲基)丙烯酸酯、藉由與(甲基)丙烯酸之加成反應而得之環氧(甲基)丙烯酸酯、2-羥基乙基(甲基)丙烯酸酯與二醇及二異氰酸酯反應而得之聚氨酯(甲基)丙烯酸酯、(甲基)丙烯酸與多元羧酸及多元醇反應而得之聚酯(甲基)丙烯酸酯聚酯丙烯酸酯、氨脂丙烯酸酯、環氧丙烯酸酯、聚醚丙烯酸酯、多元醇丙烯酸酯);或甲基丙烯酸酯類(例如,聚酯甲基丙烯酸酯、氨酯甲基丙烯酸酯、環氧甲基丙烯酸酯、聚醚甲基丙烯酸酯、多元醇甲基丙烯酸酯)。其他,可舉丙烯酸正烷基酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸第三丁酯、丙烯酸環己酯、丙烯酸β-羥基乙酯、二甘醇丙烯酸酯、聚乙二醇丙烯酸酯、丙烯酸β-羥基丙酯、丙烯酸縮水甘油酯、乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、烷基胺基乙基丙烯酸酯、2-氰基乙基丙烯酸酯、β-乙氧基乙基丙烯酸酯、芳基丙烯酸酯、丙烯酸苄氧基乙酯、丙烯酸苄酯、丙烯酸2-苯氧基乙酯、丙烯酸苯氧基二乙二醇酯、丙烯酸2-羥基-3-苯氧基丙酯、丙烯酸四羥糠醇酯、四羥糠醇與ε-己內酯的加成物丙烯酸酯、丙烯酸異冰片酯、丙烯酸二環戊烯氧乙酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,9-壬二醇酯二丙烯酸、新戊二醇二丙烯酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、羥基新戊酸新戊二醇二丙烯酸酯、縮乙醛二醇二丙烯酸酯、羥基新戊酸新戊二醇與ε-己內酯的加成物二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷.聚氧乙烯.三丙烯酸酯、三羥甲基丙烷.聚氧丙烯.三丙烯酸酯、異戊四醇三丙烯酸酯、二異戊四醇六丙烯酸酯、二異戊四醇與ε-己內酯的加成物六丙烯酸酯、丙烯醯氧乙基磷酸酯、氟烷基丙烯酸酯、磺丙基丙烯酸酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸異丙酯、甲基丙烯酸丁酯、甲基丙烯酸異丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯、甲基丙烯酸己酯、甲基丙烯酸辛酯、甲基丙烯酸異辛酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸癸酯、甲基丙烯酸月桂酯、甲基丙烯酸硬脂酯、甲基丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基丙酯、甲基丙烯酸2-二甲基胺基乙酯、甲基丙烯酸2-二乙基胺基乙酯、甲基丙烯酸2-第三丁基胺基乙酯、甲基丙烯酸縮水甘油酯、甲基丙烯酸丙烯醛酯、甲基丙烯酸環己酯、甲基丙烯酸苯酯、甲基丙烯酸壬基苯酯、甲基丙烯酸苄酯、甲基丙烯酸二環戊烯酯、甲基丙烯酸冰片酯、1,4-丁二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、二甘醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、新戊二醇二甲基丙烯酸酯、1,6-己烷二醇二甲基丙烯酸酯、二丙二醇二甲基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、甲基丙烯酸甘油酯、甲基丙烯醯氧乙基磷酸酯、雙甲基丙烯醯氧乙基磷酸酯、3-乙基-3-(苯氧基甲基)氧雜環丁烷、二[1-乙基(3-氧雜環丁基)]甲醚、3-乙基-3-(己氧基甲基)氧雜環丁烷、二甲苯氧雜環丁烷、苯基氧雜環丁烷、苯基氧雜環丁基聚倍半矽氧烷、3-乙基-3-(庚氧基甲基)氧雜環丁烷、3-乙基-3-(2-乙基己氧基甲基)氧雜環丁烷、3-乙基3-(辛氧甲基)氧雜環丁烷、3-乙基3-(十二烷氧基甲基)氧雜環丁烷、雙酚A型環氧單體、雙酚F型環氧單體、甲酚型環氧單體、甲苯二異氰酸酯等。
於上述聚合起始劑、架橋劑、架橋促進劑或架橋助劑,可使用各種者。例如過氧化物類、陽離子聚合起始劑、光聚合起始劑、硫系架橋促進劑、多元醇系架橋劑、聚胺系架橋劑、聚硫醇系架橋劑、丙烯酸酯系架橋助劑、甲基丙烯酸酯系架橋助劑、丙烯酸系架橋助劑等。具體而言,例如偶氮雙丁腈、二苯甲酮、米氏酮、安息香異丙醚、氯噻噸酮、異丙基噻噸酮、二甲基苄基酮、苯乙酮二乙酮、α-羥基環己基苯基酮、2-羥基-2-甲基-苯基丙烷等。亦可舉苯乙酮衍生化合物(例如,4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α’-二甲基苯乙酮、甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮)。亦可舉安息香醚系化合物(例如,安息香醚乙醚、安息香醚丙醚)。亦可舉二甲基苄基酮等的酮衍生化合物。亦可舉鹵化酮、酰基膦氧化合物、醯基磷酸酯、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基膦氧化合物、苯基二甲基氯化鋶、三芳基六氟磷酸鋶。亦可舉三嗪二硫醇系架橋劑、樹脂架橋劑、多元醇架橋劑、H末端矽氧烷系架橋劑、矽醇縮合系架橋劑。二硫代二苯並噻唑、4-嗎啉基二硫代苯並噻唑、N-環己基-2-苯並噻唑次磺醯胺、N-第三丁基-2-苯並噻唑次磺醯胺、N-氧二亞乙基-2-苯並噻唑次磺醯胺、N-二異丙基-2-苯並噻唑次磺醯胺、N-二環己酯-2-苯並噻唑次磺醯胺、二硫代四甲基秋蘭姆、二硫代四乙基秋蘭姆、二硫代四丁基秋蘭姆、二硫代四辛基秋蘭姆、胺類、六亞甲基四胺、羰基硫、四級銨鹽、鏻鹽、二烷基錫有機酸鹽、鈦酸鹽、聚乙二醇、氯化鉑酸、氧化鋅、氧化鎂、氧化鈣、氧化鋇、氧化鋁、氫氧化鈣、氧化錫、氧化鐵、氫氧化鈣、碳酸鈣、碳酸鎂、脂肪酸鈉、辛酸鈣、異辛酸鉀、異丁基氧化鉀、辛酸銫、異硬脂酸鉀、聚乙二醇、聚丙二醇、己二醇、環己二醇、十二烷二醇、六亞甲基二胺、十二烷二胺、末端二胺基聚乙二醇、末端二胺基聚丙二醇、苯二硫醇、己二硫醇、1,10-癸二硫醇、1,12-十二烷二硫醇、聚乙二醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、聚丙二醇二丙烯酸酯、聚丙二醇二甲基丙烯酸酯、二烯丙醚、三烯丙基異氰酸酯、三烯丙基氰酸酯等。
高分子材料之二維線狀構造聚合物(熱塑性樹脂、未架橋橡膠)與三維網眼構造的聚合物(熱硬化性樹脂、架橋橡膠)製的基體,係對100重量部的二維線狀構造的聚合物(或,單體),未添加架橋劑(二維線狀構造聚合物,熱塑性樹脂)或添加0.1~20重量部的架橋劑、0.1~20重量部的架橋促進劑、及0.1~20重量部的架橋助劑之組合物,以溫度20~350℃、加工時間以0.1秒~200分鐘的條件,進行輥輪壓片加工、淋幕輥輪加工、層壓加工、擠出加工、或射出成形加工而。惟,根據加工機的特性,架橋劑等添加量、加工溫度、加工時間不同。
基體以光硬化樹脂構成時,可使用UV裝置(例如,高壓水銀UV燈、低壓水銀UV燈、螢光式UV燈(短ARC氙氣燈、化學燈)、金屬鹵化物燈),以200~450nm的紫外線,於所期望的環境下,例如大氣下、氮氣氣氛下、氬氣氣氛下或減壓下)照射而得。照射光量,例如為1mJ/m2
~20J/m2
。適宜選定照射紫外線的組合物。例如,包含100重量部的環氧系化合物與0.01~5重量部的光聚合觸媒的組合物。
加硫橡膠,係將包含選自由玻璃轉移溫度為-20℃以下的線狀聚合體之群之一種或二種以上彈性體,與添加劑(例如架橋劑、架橋促進劑等)的組合物,以0~300℃的溫度保持0.1~1200分鐘而得。加成型矽酮橡膠或縮合型矽酮橡膠等,有以低溫長時間加熱而得之情形。溫度一般以60~180℃之情形為多。
於上述基體,按照需要,可以適宜的量含有各種的填充劑和增強劑。例如按照需要,各種碳黑、碳酸鈣、滑石、黏土、高嶺土、玻璃、濕式二氧化矽、乾式二氧化矽。按照需要,可包含嫘縈、尼龍、聚酯、維尼龍、鋼絲、克維拉,碳纖維、玻璃纖維、布。必要按照,可包含金屬粒子(銅、鎳、銀、金、錫等)。按照需要,可包含碳粒子。按照需要,可包含導電性材料。按照需要,可包含氧化鋁、氮化矽、氮氧化鋁、碳化矽、鑽石等傳熱材。含量,對聚合物100重量部,為200重量部以下。一般為100重量部以下。惟,亦有按照需要,含有較200重量部多之情形。
於上述基體,按照需要,可含有適宜的量的穩定劑。穩定劑,係例如老化防止劑或紫外線吸收劑。可舉例如,聚(2,2,4-三甲基-1,2-二氫喹啉)、6-乙氧基1,2-二氫-2,2,4-三甲基喹啉等的胺‧酮系縮合物。辛基二苯胺、4,4-雙(α,α-二甲基苄基)二苯胺、N,N-二苯基-對苯二胺、N-苯基-N’-異丙基對苯二胺、N-苯基-N’-異丙基-1,3-二甲基丁基對苯二胺等芳香族二級胺化合物。苯乙烯化酚、2,6-第三丁基-4-酚、2-第三丁基-6-(3-第三丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2,2-亞甲基雙(4-甲基-6-第三丁基酚)、4,4-硫代雙(3-甲基-6-第三丁基酚)-2,5-第三丁基氫喹啉等單一或雙酚系化合物。2-胇基苯並咪唑、2-Zn胇基苯並咪唑、鎳二甲基二硫代胺基甲酸酯、1,3-雙(二甲基胺基丙基)硫代尿素、二月桂基-3,3-硫代二丙酸酯、三(壬基化苯基)磷酸酯等的硫系或磷系化合物。含量,對聚合物100重量部,為30重量部以下。一般為0.5~5重量部。
於上述基體,按照需要,可含有適宜的量以下化合物。例如,對甲氧基桂皮酸2乙基己酯(辛酯)、對二甲基胺基安息香酸2乙基己酯(辛酯)、羥苯甲酮(二苯甲酮)、水楊酸2乙基己酯、4-第三丁基-4-甲氧基苯甲醯甲烷、苯甲酸酯系穩定劑、受阻胺系光穩定劑等紫外線吸收材料。含量,對聚合物100重量部為10重量部以下。一般為0.1~2重量部
上述基體,按照需要,可含有適宜量的軟化劑、可塑劑、加工助劑、黏度調整劑、著色劑。
[基體的表面處理]
首先,準備溶解或分散上述化合物(α)的溶液。使用之溶劑,係水、醇(例如甲醇、乙醇、異丙醇、乙二醇、丙二醇、溶纖劑、卡必醇)、酮(例如,丙酮、甲乙酮、甲基環己酮)、芳香烴(例如,苯、甲苯、二甲苯)、脂肪烴(例如,己烷、辛烷、癸烷、十二烷、十八烷)、酯(例如,醋酸乙酯、丙酸甲酯、鄰苯二甲酸甲酯)、醚(例如,四氫呋喃、乙基丁基醚、茴香醚)等。亦可為上述化合物的混合物。上述化合物(α)的含量為0.0001~10wt%。特別是以0.001~2wt%為佳。此係,上述化合物(α)含量過少,則缺乏效果。相反地,與基體的反應量有所限定,過多缺乏意義。由如此之觀點,以上述比例為佳。
上述溶液(分散液)中,按照需要,由調整表面張力的觀點,可添加界面活性劑。可使用例如,非離子系界面活性劑(例如,長鏈烷基鏈與聚乙二醇所組成的非離子系界面活性劑)、陽離子系界面活性劑(例如,4級銨鹽)、或陰離子系界面活性劑(例如,有機羧酸鹽、硫酸鹽)。
將基體浸漬於上述溶液(分散液)中。或,將上述溶液(分散液)對基體噴霧。藉此,可使上述接著性提升劑(上述化合物(α):分子接著劑)附著於基體表面。
之後,做光(紫外線)照射。特別是僅於欲使上述化合物(α)與上述基體鍵結之處做光照射。為此,使用適宜圖案的光罩。藉由上述紫外線照射,使上述化合物(α)的疊氮基分解。藉由疊氮基的分解,生成氮烯。該氮烯,將攻擊上述基體表面的官能基(例如-CH3
、-CH2
、-CH<、-CH=CH-)。然後,發生拔氫自由基加成或自由基加成反應,於上述化合物(α)與基體表面之間發生化學鍵結。於未照射處,並不會發生化學鍵結。
於紫外線照射,使用UV裝置(例如高壓水銀UV燈、低壓水銀UV燈、螢光式UV燈(短ARC氙氣燈、化學燈)、金屬鹵化物水銀燈)。然後,照射200~450nm的紫外線。照射光量過少,則難以進行反應。相反地,照射光量過多,則有損及基體之虞。因此,照射光量(波長254nm)以1mJ/m2
~5J/m2
為佳。以5mJ/m2
-1J/m2
更佳。
在於基體為複雜的形狀時,為對基體均一地照射UV,使用反射板有效。反射板,可舉例如鏡子、表面研磨之金屬箔、Al鏡面箔、SUS鏡面箔、銀鍍敷鏡面板等。由反射效率的觀點,適宜選擇反射板的形狀、尺寸、材質等。
上述紫外線照射後的基體係以水處理。例如,浸漬於水中。水,以酸性水溶液或鹼性水溶液為佳。例如將基體浸漬於0.0001~10%(以0.01~5%為佳)的酸性水溶液,0.1~60分鐘(以1~20分鐘)。藉此,烷氧基矽基變性為羥基矽基。上述數值條件,係根據由烷氧基矽基變性為羥基矽基之效率的觀點。
加上上述化合物(α),並用上述通式[II]的聚合物為佳。即,藉由並用上述通式[II]的聚合物,可增加存在於基體表面的-OH的數量。即,藉由使用上述通式[II]的含有烷氧基之聚合物,可增加存在於表面之-OH的數量。
以上述含有烷氧基之聚合物之處理,可與以上述化合物(α)之處理同樣地進行。即以含有(溶解或分散)上述通式[II]的聚合物溶液處理基體。用於上述處理之溶劑,水、醇(例如甲醇、乙醇、異丙醇、乙二醇、丙二醇、溶纖劑、卡必醇)、酮(例如,丙酮、甲乙酮、甲基環己酮)、芳香烴(例如,苯、甲苯、二甲苯)、脂肪烴(例如,己烷、辛烷、癸烷、十二烷、十八烷)、酯(例如,醋酸乙酯、丙酸甲酯、鄰苯二甲酸甲酯)、醚(例如,四氫呋喃、乙基丁基醚、茴香醚)等。亦可為上述化合物的混合物。上述通式[II]的聚合物的含量為0.0001~10wt%。特別是以0.001~5wt%為佳。此係,上述聚合物的含量過少,則缺乏效果。於上述聚合物之處理之後,以0~200℃(以20~150℃為佳)加熱處理0.1~60分鐘(1~20分鐘)。
此外,加上使用上述化合物(α),以上述通式[T][111]或/及[IV]所示的化合物處理亦佳。即,藉由並用上述通式[T][111]或/及[IV]所示的化合物,可將存在於基體表面的-OH的數量增加。再者,可導入反應性官能基。
以上述通式[T][111]或/及[IV]所示的化合物之處理,係進行與以上述化合物(α)相同的處理。即以含有(溶解或分散)上述通式[T][111]或/及[IV]所示化合物溶液處理基體。用於上述處理之溶劑,水、醇(例如甲醇、乙醇、異丙醇、乙二醇、丙二醇、溶纖劑、卡必醇)、酮(例如,丙酮、甲乙酮、甲基環己酮)、芳香烴(例如,苯、甲苯、二甲苯)、脂肪烴(例如,己烷、辛烷、癸烷、十二烷、十八烷)、酯(例如,醋酸乙酯、丙酸甲酯、鄰苯二甲酸甲酯)、醚(例如,四氫呋喃、乙基丁基醚、茴香醚)等。亦可為上述化合物的混合物。上述通式[111]或[IV]所示的化合物的含量為0.0001~10wt%。特別是以0.001~5wt%為佳。此係,上述聚合物的含量過少,則缺乏效果。上述通式[T][111]或/及[IV]所示的化合物的處理之後,以0~200℃(以20~150℃為佳)加熱處理0.1~60分鐘(1~20分鐘)。
於本發明,在於步驟(U),可使用例如具有烷氧基矽基的偶合劑。藉此,可對基體表面導入各種官能基。該等偶合劑,可舉例如,6-烷氧基矽基丙基胺基-1,3,5-三嗪-2,4-二硫醇一鈉、6-雙(3-烷氧基矽基丙基)胺基-1,3,5-三嗪-2,4-二硫醇一鈉、6-N-環己基-N-(3-(三乙氧基矽基)丙基胺基)-1,3,5-三嗪-2,4-二硫醇一鈉、乙烯基甲氧基矽氧烷均聚物、雙(三乙氧基矽基丙基)四硫化物、3-胇基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、6-烷氧基矽基丙基胺基-1,3,5-三嗪-2,4-二硫醇、3-烷氧基矽基丙基胺、雙(3-烷氧基矽基丙基)胺、6-N-環己基-N-3-(三乙氧基矽基)丙基胺、3-胺基丙基三乙氧基矽烷、(3-丙烯醯氧丙基)三甲氧基矽烷、甲基丙烯醯氧丙基三甲氧基矽烷、三乙氧基矽基十一醇、4-胺基丁基三乙氧基矽烷、間胺基苯基三乙氧基矽烷、11-胺基十一烷基三甲氧基矽烷、N-(3-三乙氧基矽基丙基)吡咯、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基甲基二乙氧基矽烷、胺基丙基矽烷三醇、N-(2-胺基乙基)-3-胺基丙基矽烷三醇、N-甲基胺基丙基三甲氧基矽烷、N-丁基胺基丙基三甲氧基矽烷、N-三甲氧基矽基丙基三甲基氯化銨、雙(三甲氧基矽基丙基)胺、3-(三乙氧基矽基)丙基琥珀酸酐、6-疊氮硫醯基己基三乙氧基矽烷、2-(4-氯硫醯基)乙基三乙氧基矽烷、2-(3,4-環氧環己基)三甲氧基矽烷、(3-縮水甘油醚氧丙基)三甲氧基矽烷、10-(甲酯基)癸基二甲基甲氧基矽烷、3-氯丙基三甲氧基矽烷、7-溴庚基三甲氧基矽烷、3-異氰酸酯基丙基三乙氧基矽烷、(3-三乙氧基矽基)-第三丁基胺基甲酸酯、2-(二苯基膦)乙基三乙氧基甲矽烷、二乙基磷酸酯三乙氧基矽烷、3-胇基丙基三甲氧基矽烷、5-(二環庚烯基)三乙氧基矽烷、(3-環戊二烯丙基)三乙氧基矽烷等。
以該等的偶合劑之處理,亦與以上述化合物(α)之處理或以上述含有烷氧基之聚合物之處理同樣地進行。用於上述處理之溶劑,水、醇(例如甲醇、乙醇、異丙醇、乙二醇、丙二醇、溶纖劑、卡必醇)、酮(例如,丙酮、甲乙酮、甲基環己酮)、芳香烴(例如,苯、甲苯、二甲苯)、脂肪烴(例如,己烷、辛烷、癸烷、十二烷、十八烷)、酯(例如,醋酸乙酯、丙酸甲酯、鄰苯二甲酸甲酯)、醚(例如,四氫呋喃、乙基丁基醚、茴香醚)等。上述偶合劑的含量為0.0001~10wt%。特別是以0.001~5wt%為佳。此係,上述偶合劑的含量過少,則缺乏效果。以上述偶合劑之處理之後,以0~200℃(以20~150℃為佳)加熱處理0.1~60分鐘(1~20分鐘)。
[金屬膜(鍍敷膜)]
於以既定圖案設置化合物(α)之基體上,設置金屬薄膜。於金屬薄膜之形成,採用無電電鍍及電鍍之濕式鍍敷手法。以該濕式鍍敷之金屬膜之形成,使用含有上述膜之金屬成分(金屬離子)之溶液(無電電鍍液或電鍍液)。
於上述無電電鍍步驟或電鍍步驟之前,一般進行以金屬觸媒溶液之處理。於付與觸媒金屬之後,亦可使用導電化步驟。於上述金屬觸媒溶液,包含例如一種或兩種類以上的金屬(例如Sn、Pd、Ag、Au、Sn/Pd、Ag/Pd、Sn/Ag/Pd等等)的鹵化物(氯化物、溴化物、碘化物)。其他,包含例如HCl等。包含Cu離子。將設有上述化合物(α)之基體浸漬於上述金屬觸媒溶液。處理條件,係例如以0~80℃(以20~50℃為佳),1~5分鐘。於電鍍或無電電鍍之前進行之本處理已習知,故省略詳細說明。該前處理並非限定於習知之技術者。
於無電電鍍液包含金屬鹽及還原劑。無電電鍍液,已知例如無電Ni-P鍍液、無電Ni-B鍍液、無電Ni-P複合鍍液、無電電鍍銅福馬林液、無電銅乙醛酸液、無電銅次亞磷酸液、無電鈀鍍液、無電金鍍液、無電鈷鍍液等。
包含於上述無電電鍍液之金屬鹽,係例如,銀、銅、金、鋅、鎳、鈷、鐵、鈀、鉑、黃銅、錫、鉬、鎢、鎳鐵合金、鋼等的金屬鹽。具體而言,可舉KAu(CN)2
、KAu(CN)4
、Na3
Au(SO3
)2
、Na3
Au(S2
O3
)2
、NaAuCl4
、AuCN、Ag(NH3
)2
NO3
、AgCN、AgNO3
、CuSO4
‧5H2
O、CuEDTA、NiSO4
‧7H2
O、NiCl2
、Ni(OCOCH3
)2
、CoSO4
、CoCl2
、SnCl2
‧7H2
O、PdCl2
等。金屬鹽的濃度係0.001~10mol/L(以0.01~1mol1/L為佳)。
上述還原劑,係具有將上述金屬鹽還原生成金屬之作用之化合物。具體而言,可舉KBH4
、NaBH4
、NaH2
PO2
、(CH3
)2
NH‧BH3
、NH2
NH2
、H2
NNH2
‧H2
O4
S、H2
NNH2
‧HCl、H2
NNH2
‧2HCl、H2
NNH2
‧CH3
COOH、羥胺鹽、N,N-乙基甘胺酸、甘醇酸鈉、乙醛酸、葡萄糖、甲醛、香草醛。還原劑濃度為0.001~5mol/L(以0.01~1mol/L)。
於上述金屬鹽或還原劑之外,亦可包含錯化劑、pH調整劑等的各種添加劑。例如,由無電電鍍液之穩定性(壽命),及還原效率的觀點而包含添加劑。具體而言,係鹼性化合物、無機鹽、有機酸鹽、檸檬酸鹽、醋酸鹽、硼酸鹽、碳酸鹽、氫氧化銨、EDTA、二胺基乙烯、酒石酸鈉、乙二醇‘、二甘醇、三乙二醇、聚乙二醇(分子量:200~400)、硫代尿素、三嗪硫醇、三乙醇胺等。添加劑濃度0.00001~10mol/L(以0.0001~1mol/L為佳)。
於電鍍液包含金屬鹽。電鍍液,已知例如,硫酸銅標準鍍液、高均一性酸性銅鍍液、氰化銅鍍液、光澤氰化銅鍍液、氰化銅打底鍍液、焦磷酸銅標準鍍液、焦磷酸銅印刷基板用鍍液、焦磷酸銅裝飾用鍍液、鎳標準鍍液、鎳瓦特鍍液、光澤鎳標準鍍液、磺胺酸鎳鍍液、六價鉻標準鍍液、三價鉻標準鍍液、鋅鹼性鍍液、氯化鋅鍍液、氰化鋅鍍液、硫酸錫鍍液、甲烷硫酸錫鍍液、鹼性錫鍍液、中性錫鍍液、弱酸性金鍍液、強酸性金鍍液、中性金鍍液、鍍金鹼性氰液、鍍金鹼性亞硫酸液、銀打底鍍液、氰化銀鍍液、硫代硫酸銀液、琥珀酸銀鍍液、鉑鍍液、銠鍍液、鈀鍍液等。當然,並不限於該等。
於電鍍液,於上述金屬鹽之外,亦可包含礦酸、鹼、平滑劑、光澤劑、抑制劑等的添加劑。具體而言,硫酸、鹽酸、硼酸、氰化鈉、苛性鉀、氨、硝酸鉀、焦磷酸鉀、洛捷爾鹽、硫氰化鉀、糖精、香豆素、苯磺酸、對甲苯磺酸、烯丙基磺酸、乙烯氰醇、吡啶丙基磺酸鹽、萘磺酸、1,4-丁烷硫醇、鉛化合物、葡糖酸鈉、氧化羧酸、界面活性劑、乙二醇、二甘醇、三乙二醇、聚乙二醇(分子量:200~600)等。
進行電鍍處理之溫度(浴溫度),係例如20~100℃(以20~70℃為佳)。電流密度,係例如0.1~15A/dm2
(以1~7A/dm2
為佳)。
使用本發明製作電路基板時,Cu配線膜等的金屬膜的形成簡單。因為,設於基板(基體)上之上述化合物(α)容易形成圖案。並且,在沒有上述化合物(α)的區域,以濕式鍍敷手法設置之金屬膜可簡單地去除。
以下,舉具體的實施例說明。惟,本發明並非受限於下述實施例。
[化合物α(-OH付與劑)的合成方法]
[合成例A-1]
於0~5℃,將0.1mol(18.4g)的三聚氰氯,加入200ml的丙酮水溶液。將含有0.204mol NaN3
的水溶液100ml,邊攪拌滴入,該三聚氰氯溶液。結束滴入後,亦繼續攪拌30分鐘。之後,由該混合溶液,用醚萃取有機層。然後,進行過濾。
之後,以旋轉濃縮機,去除醚。接著,藉由減壓乾燥,得到粗生成物。藉由矽膠管柱層析儀(沖提溶劑:混合溶劑(氯仿:己烷=1:2))進行純化。所得純化物係油狀。其量為18.1g(產率:91.5%)。
將所得純化物(化合物)的鑑定,係以元素分析測定裝置、NMR測定裝置及MS測定裝置進行。結果,確定為純化物係2,4-二疊氮-6-氯1,3,5-三嗪(DAMC)。
元素分析測定裝置係珀金埃爾默2400CHN型分析裝置。
NMR測定裝置係日本布魯克公司製AC400P。MS測定裝置係JEOL JMS-700。以下使用的元素分析測定裝置、NMR測定裝置、MS測定裝置係與上述裝置相同的裝置。
DAMC
13
C NMR(101MHz,CDCl3
) d 171.4,172.6
EI-MS(70eV)m/z197(M+)
元素分析(實測值/計算值)C:18.3/18.24,N:63.6/63.81
將上述DAMC9.88g(0.050mol)加入四氫呋喃(THF)100ml。之後,置於氮氣氣氛下。對該DAMC溶液,滴入含有0.050mol(11.5ml)的三乙氧基矽基丙基胺與0.051mol(7.2ml)的三乙胺之THF溶液100ml。然後,於50℃下進行攪拌120分鐘。反應結束之後,去除生成之三乙胺鹽酸鹽。於減壓下(20mmHg)去除THF得到粗生成物。
以矽膠管柱層析儀(沖提溶劑:氯仿)進行純化。所得純化物係白色粉末。其量為18.55g(產率:97%)。
將所得純化物(化合物)的鑑定,係以元素分析測定裝置、NMR測定裝置及MS測定裝置進行。結果,確定純化物為6-(3-三乙氧基矽基丙基)胺基-1,3,5-三嗪-2,4-二疊氮(TE-DAZ)。
TE-DAZ
1
H NMR(400 MHz,CDCl3
) δ 0.67(t,J=8.0Hz,2H,CH2CH2Si),1.23(t,J=7.0 Hz,9H,SiOCH2CH3),1.73(quint,2H,CH2CH2CH2Si),3.46(q,J=8.0 Hz,2H,NHCH2CH2CH2),3.83(q,J=7.0 Hz,6H,SiOCH2CH3),6.36(br s,1H,NHCH2CH2CH2)
13
C NMR(101 MHz,CDCl3) δ 7.7,18.2,22.5,43.4,58.5,166.8,169.6,170.3,EI-MS(70 eV) m/z 382(M+)。
元素分析(實測值/計算值) C:37.4/37.69,H:5.9/5.80,N:36.9/36.62
[合成例A-2]
依照上述[合成例A-1]進行。
即,在於上述[合成例A-1],取代0.050mol(11.5ml)三乙氧基矽基丙基胺,使用0.050mol(21.9ml)雙(3-三乙氧基矽基丙基)胺以外同樣地進行。所得純化物係油狀。其量為28.17g(產率:96%)。
將所得純化物(化合物)的鑑定,係以元素分析測定裝置、NMR測定裝置及MS測定裝置進行。結果,確定純化物為6-雙(3-三乙氧基丙基)胺基-1,3,5-三嗪-2,4-二疊氮(BTE-DAZ)。
BTE-DAZ
1
H NMR(400 MHz,CDCl3
) d 0.59(t,J=8.0 Hz,4H,CH2CH2Si),1.22(t,J=6.9 Hz,18H,SiOCH2CH3),1.66-1.74(m,4H,CH2CH2Si),3.53(t,8.0Hz,4H,NCH2
CH2
),3.82(q,J=6.9 Hz,12H,SiOCH2CH3),
13
C NMR(101 MHz,CDCl3) d 7.6,18.3,20.9,50.2,58.4,165.3,169.8
EI-MS(70 eV) m/z 586(M+)
元素分析(實測值/計算值) C:43.2/42.98,H:7.3/7.21,N:23.6/23.87
[合成例A-3]
依照上述[合成例A-1]進行。
即,在於上述[合成例A-1],使用0.102mol的NaN3
以外同樣地進行。所得純化物是油狀。其量為17.2g(產率:90%)。
將所得純化物(化合物)的鑑定,係以元素分析測定裝置、NMR測定裝置及MS測定裝置進行。結果,確定純化物為2-疊氮-4,6-二氯-1,3,5-三嗪、(MADC)。
MADC
13
C NMR(101 MHz,CDCl3) d 171.5,172.8
EI-MS(70eV)m/z190(M+)
元素分析(實測值/計算值)C:18.5/18.87,N:44.3/44.01
將上述MADC4.35g(0.023mol)加入四氫呋喃(THF)50ml。然後,置於氮氣氣氛下。對該MADC溶液,滴入含有0.048mol(11ml)胺基丙基三乙氧基矽烷的THF溶液40ml。之後,滴入含有048mol(6.8ml)的三乙胺的THF溶液40ml。結束滴入後,將反應溶液升溫至45℃。之後,進行攪拌1小時。進行冷卻至室溫。由於有銨鹽析出,故以抽氣過濾進行過濾。濾液以旋轉濃縮機濃縮。藉由減壓乾燥得到粗生成物。純化係以矽膠管柱層析儀(沖提溶劑:混合溶劑(醋酸乙酯:己烷=1:2))進行。所得純化物係無色的油狀。其量為10.86g(產率:85%)。
將所得純化物(化合物)的鑑定,係以元素分析測定裝置、NMR測定裝置及MS測定裝置進行。結果,確定純化物為2-疊氮-4,6-雙(3-三乙氧基矽基丙基)胺基-1,3,5-三嗪(TE-MAZ)。
TE-MAZ
1
H NMR(400 MHz,CDCl3
) d 0.66(t,J=8.0 Hz,4H,CH2
CH2
Si),1.23(t,J=7.0Hz,18H,SiOCH2
CH3
),1.69(br s,4H,CH2
CH2
CH2
Si),3.34-3.42(m,4H,NCH2
CH2
),3.82(q,J=7.0Hz,12H,SiOCH2
CH3
),5.40,5.54,及5.64(br s×3,2H,NHCH2
)
FAB-MS m/z 561(M+1);
元素分析(實測值/計算值) C:45.1/44.98,H:8.2/7.91,N:20.1/19.98
[實施例1]
[步驟(X)]
準備ABS樹脂製的基板。將該基板以40℃的乙醇中超音波清洗10分鐘。超音波清洗之後,浸漬於化合物TE-DAZ之乙醇溶液(濃度2mmol)(溫度:20℃,時間:5分鐘)。將基板拉起後,乾燥之。
[步驟(W)]
於步驟(X)之後,對上述基板施以紫外線照射。於該紫外線照射時,例如係為沿著配線圖案者,故使用既定圖案的光罩。紫外線照射裝置,係高壓水銀燈(Eye Graphic公司製的EYE mini grandage,輸出:2kw、照射能量:30mJ/cm2
)。上述紫外線照射後,以乙醇清洗上述基板。
[步驟(Y)]
上述步驟(W)之後,將上述基板,浸漬於觸媒處理液(上村工業株式會社製NP-8;150ml/L,HCI;150ml/L)中(溫度:25℃,時間:1分鐘)。藉此,於表面擔持Pd-Sn觸媒。將該擔持Pd-Sn觸媒之基板,浸漬於無電電鍍銅浴(上村工業株式會社製之THRU-CUP PSY-1A;100ml/L THRU-CUP PSY-1B;55ml/L 18.5%福馬林水溶液;20ml/L)中((溫度:33℃、時間:20分鐘)。藉此,於表面形成厚度0.2μm的Cu鍍敷膜。
[實施例2]
依照上述實施例1進行。即,於上述實施例1,取代TE-DAZ使用BTE-DAZ以外同樣地進行。
[實施例3]
依照上述實施例1進行。即,於上述實施例1,取代TE-DAZ使用TE-MAZ以外同樣地進行。
[比較例1]
依照上述實施例1進行。即,於上述實施例1,取代TE-DAZ使用TE-ASH(疊氮磺酸己基三乙氧基矽烷)以外同樣地進行。
[特性]
對上述實施例1~3及比較例1所得之樣品,進行下述測定,將其結果示於表-1。
在於表面層(深度:8nm)之元素組成,係以X射線光電子光譜裝置(ULVACPHI公司:PERKIN ELMER PHI 5600 ESCA)測定。
接觸角係以接觸角測定裝置(Elma-type G-1)測定。
Cu鍍敷接著性,係如下調查。對上述樣品切入切痕(向縱‧橫方向以1mm的間隔10條)。即,合計形成100個□。對此,黏貼膠帶(住友3M公司製:Scotch隱形膠帶)後,剝離。數此時之剝離數。
*在於接觸角及在剝離數之數值中,( )外的數值,係於進行紫外線照射之處的接觸角及剝離數,( )內的數值係於未進行紫外線照射之處之接觸角及剝離數。
由表-1,可之藉由對付有化合物(α)之基板進行紫外線照射,由化合物(α)的疊氮基所產生的氮烯,與樹脂基板的C-H基或C=C基之間發生加成反應,使化合物(α)鍵結於樹脂基體的表面。即,可知於基板表面存在烷氧基矽基。ABS樹脂,原本就具有4原子%來自丙烯腈之N。但是,本實施例,均較該數值為高的值。即,可知三嗪環有鍵結於ABS樹脂表面。
於表面鍵結化合物(α)之樹脂基板,接觸角小。但是,未進行紫外線照射之處的接觸角大。由此,可知在沒有進行紫外線照射之處,可藉由乙醇清洗,去除化合物(α)。
藉由無電電鍍,於基板表面,形成Cu膜。該Cu鍍敷膜,在藉由紫外線照射使化合物(α)鍵結於樹脂基板上之處,密著強度高。
由此,可知本實施例的技術可良好地用於汽車、建材、日用品用創意(裝飾)製品、藉由半添加法之電路基板。當然,應可理解亦可使用於該等以外之製品。
[實施例4~6]
首先,依照上述實施例1~3進行。但,在無電電鍍銅浴中的浸漬時間為10分鐘。因此,所形成的無電電鍍Cu膜的厚度為0.1μm。
之後,進行電鍍。使用於該電鍍之電解浴,係上村工業株式會社製的THRU-CUP ETN浴(CuSO4
‧5H2
O;80g/L;H2
SO4
;200g/L,Cl-
;50ppm)、THRU-CUP ETN-1A浴(1ml/L)、THRU-CUP ETN-1B浴(10ml/L)。
電流為2.5A/dm2
。時間為120分鐘。溫度為25℃。如此所得之Cu鍍敷膜的厚度為30μm。
[比較例2]
首先,依照上述比較例1進行。但,在無電電鍍銅浴中的浸漬時間為為10分鐘。
之後,進行電鍍。使用於該電鍍之電解浴,係上村工業株式會社製的THRU-CUP ETN浴(CuSO4
‧5H2O;80g/L;H2SO4;200g/L,Cl-
;50ppm)、THRU-CUP ETN-1A浴(1ml/L)、THRU-CUP ETN-1B浴(10ml/L)。
電流為2.5A/dm2
。時間為120分鐘。溫度為25℃。
[特性]
對上述實施例4~6及比較例2所得的樣品,進行下述測定,將其結果示於表-2。
於XPS分析的測定,使用用於上述實施例1之測定之裝置。
Cu鍍敷膜的密著強度的測定,使用剝離試驗裝置(島津製作所製的Autograph P-100)。測定時的剝離速度係50mm/min的條件。
可理解本實施例的Cu鍍敷膜密著強度非常大。由此,可知本實施例的技術可良好地用於汽車、建材用、日用品用創意(裝飾)製品、藉由半添加法之電路基板。當然,應可理解亦可使用於該等以外之製品。
[實施例7~22]
依照實施例4進行。惟,於本實施例係使用EP(環氧)樹脂製基板、PET(聚脂)樹脂製基板、PA6(6-尼龍)樹脂製基板、PI(聚醯亞胺)樹脂製基板、ABS樹脂製基板、PC(聚碳酸酯)樹脂製基板、PSt(聚苯乙烯)樹脂製基板、PE(聚乙烯)樹脂製基板、PP(聚丙烯)樹脂製基板、COP(環烯烴聚合物)樹脂製基板、PPS(聚苯硫醚)樹脂製基板、PEEK(聚醚酮)樹脂製基板、NBR(丁腈橡膠)基板、FKM(氟橡膠)基板、Q(矽酮橡膠)基板、SBR(苯乙烯丁二烯橡膠)基板。
[比較例3~18]
依照比較例2進行。惟,於本比較例係使用EP樹脂製基板、PET樹脂製基板、PA6樹脂製基板、PI樹脂製基板、ABS樹脂製基板、PC樹脂製基板、PSt樹脂製基板、PE樹脂製基板、PP樹脂製基板、COP樹脂製基板、PPS樹脂製基板、PEEK樹脂製基板、NBR基板、FKM基板、Q基板、SBR基板
[特性]
調查所得30μm厚的Cu鍍敷膜的密著強度,將其結果示於表-3。亦進行熱衝擊試驗,將其結果示於表-3。
*密著強度:依據JISK6854測定。即,首先,以1cm寬幅切入切痕。由邊剝離至2cm的位置,以島津Autograph P-100,以50mm/min的速度進行T字型剝離試驗。
*熱衝擊試驗:使用冷熱衝擊試驗裝置(ESPEC公司製的TSA-71H-W)。然後,將基板置於如下環境(85℃(60分鐘)→常溫(60分鐘)→-40℃(30分鐘)→常溫(30分鐘)→85℃(60分鐘)的3循環)後,基板表面以肉眼觀察。
根據此,可知以本實施例的Cu鍍敷膜密著強度優良。
首先,將PE樹脂製基板,浸漬於TE-DAZ乙醇溶液中(第
1處理)。之後,進行紫外線照射。接著,將上述基板,浸漬於聚二乙氧基矽烷(PDES)溶液及/或6-三乙氧基矽基丙基胺基-1,3,5-三嗪-2,4-二硫醇鈉(TES)溶液中(第2處理)。然後,進行乙醇清洗。藉此,得到供於無電電鍍基板。即,使用經由上述處理之基板,依照實施例1,設置無電電鍍膜及電鍍膜。
如此所得之30μm厚之Cu鍍敷膜的密著強度,遵照JISK6854調查,將其結果示於表-4。
可知藉由本實施例,以化合物(α)處理之後,亦以上述通式[II][III][IV]所示的化合物處理,則金屬膜的密著強度變得更高。
於-10℃下,將0.1mol(18.4g)的三聚氰氯,加入200ml的THF溶液。然後,置於氮氣氣氛下。對該三聚氰氯溶液,滴入含有0.105mol(35.0g)的11-胺基十一烷基三乙氧基矽烷與0.105mol(14.6ml)之三乙胺之THF溶液100ml。結束滴入後,持續進行攪拌30分鐘。反應結束後,去除產生的三乙胺鹽酸鹽。於減壓下(20mmHg)餾除THF,得到粗生成物。藉由矽膠管柱層析儀進行純化。所得純化物係油狀。其量為43.05g(產率:89.4%)。
將所得純化物(化合物)的鑑定,係以元素分析測定裝置、NMR測定裝置及MS測定裝置進行。結果,確定純化物為6-(11-三乙氧基矽基十一烷基丙基)胺基-1,3,5-三嗪-2,4-二氯化物(TEU-DC)。
TEU-DC
1
H NMR(400 MHz,CDCl3
) d 0.63(t,J=8.0Hz,2H,CH2CH2Si),1.23(t,J=7.0Hz,9H,SiOCH2CH3),1.24-1.42(m,J=8.0Hz,16H,NHCH2CH2(CH2)8CH2),1.58(quint,J=8.0Hz,2H,NHCHCH2CH2),3.46(q,J=8.0Hz,2H,NHCH2CH2),3.81(q,J=7.0Hz,6H,SiOCH2CH3),5.82(brs,1H,NH)
13
C NMR(101 MHz,CDC13) d 10.11,18.27,22.60,26.40,29.16,29.28,29.52,29.57,33.12,41.34,58.25,166.88,169.55,170.47
EI-MS(70eV) m/z 480(M+)
元素分析(實測值/計算值) C:49.7/49.89,H:7.9/7.95,N:11.7/11.64
將上述TEU-DC24.1g(0.050mol),係於50~60℃下,加入乙醇200ml。然後,置於氮氣氣氛下。對該TEU-DC溶液,邊攪拌滴入含有0.102mol的NaN3
之乙醇50ml。結束滴入後,持續進行攪拌7小時。將析出的鹽進行過濾。之後,藉由旋轉濃縮機,去除乙醇。接著使用異丙基醇(IPA)與水,進行再沉澱。過濾析出的結晶。之後,進行乾燥。所得純化物是油狀。其量為23.5g(產率:95.2%)。
將所得純化物(化合物)的鑑定,係以元素分析測定裝置、NMR測定裝置及MS測定裝置進行。結果,確定純化物為6-(11-三乙氧基矽基十一烷基)胺基-1,3,5-三嗪-2,4-二疊氮(TEU-DAZ)。
TEU-DAZ
1
H NMR(400 MHz,CDCl3
) d 0.63(t,J=8.0Hz,2H,CH2CH2Si),1,23(t,J=7.0Hz,9H,SiOCH2CH3),1.24-1.42(m,J=8.0Hz,16H,NHCH2CH2(CH2)8CH2),1.58(quint,J=8.0Hz,2H,NHCHCH2CH2),3.46(q,J=8.0Hz,2H,NHCH2CH2),3.81(q,J=7.0Hz,6H,SiOCH2CH3),5.98(br s,1H,NH)
13
C NMR(101 MHz,CDCl3) d.10.38,18.29,22.74,26.37,29.22,29.26,29.49,29.55,33.17,41.15,58.27,166.91,169.63,170.43
EI-MS(70 eV) m/z 494(M+)
元素分析(實測值/計算值) C:48.4/48.56,H:7.8/7.74,N:28.1/28.32
[合成例A-5]
於-10℃下,將5.0g(0.027mol)的三聚氰氯,加入50ml的THF溶液。然後,置於氮氣氣氛下。對該三聚氰氯溶液,滴入含有5.2g(0.027mol)的3-胺基丙基二乙氧基甲基矽烷與3.8g(0.038mol)之三乙胺之THF溶液30ml。結束滴入後,持續進行攪拌2小時。反應結束之後,去除產生的三乙胺鹽酸鹽。於減壓下(20mmHg)餾除THF,得到粗生成物。藉由矽膠管柱層析儀進行純化。所得純化物係油狀。其量為9.19g(產率:100.0%)。將所得純化物(化合物)的鑑定,係以元素分析測定裝置、NMR測定裝置及MS測定裝置進行。結果,確定生成物為6-(3-二乙氧甲基矽基丙基)胺基-1,3,5-三嗪-2,4-二氯化物(DEM-DC)。
DEM-DC
1
H NMR(400 MHz,CDCl3
) d 0.14(s,J=8.0Hz,3H,CH2CH2SiCH3),0.65(t,J=8.0Hz,2H,CH2CH2Si),1.23(t,J=7.0Hz,6H,SiOCH2CH3),1.71(quint,J=8.0Hz,2H,NHCHCH2CH2),3.50(q,J=8.0Hz,2H,NHCH2CH2),3,77(q,J=7.0Hz,4H,SiOCH2CH3),6.72(br s,1H,NH)
13
C NMR(101 MHz,CDCl3) d. -4.99,11.18,18.33,22.35,43.85,58.32,165.79,169.65,170.85
EI-MS(70 eV) m/z 450(M+)
元素分析(實測值/計算值) C:38.8/38.94,H:6.0/5.94,N:16.5/16.51
將上述DEM-DC9.19g(0.027mol),於50~60℃下,加入甲醇100ml。然後,置於氮氣氣氛下。對該DEM-DC溶液,邊攪拌滴入含有3.8g(0.059mol)的NaN3
之甲醇50ml。結束滴入後,持續進行攪拌3小時。於減壓下(20mmHg)餾除甲醇,得到粗生成物。對該粗生成物加入醚200ml。去除生成之鹽及過剩量的NaN3
。藉由矽膠管柱層析儀進行純化。所得純化物係白色粉體。其量為9.2g(產率:93%)。
將所得純化物(化合物)的鑑定,係以元素分析測定裝置、NMR測定裝置及MS測定裝置進行。結果,確定純化物為6-(3-二乙氧甲基矽基丙基)胺基-1,3,5-三嗪-2,4-二疊氮(DEM-DAZ)。
DEM-DAZ
1
H NMR(400 MHz,CDCl3
) d 0.13(s,J=8.0Hz,3H,CH2CH2SiCH3),0.65(t,J=8.0Hz,2H,CH2CH2Si),1.22(t,J=7.0Hz,6H,SiOCH2CH3),1.69(quint,J=8.0Hz,2H,NHCHCH2CH2),3.45(q,J=8.0Hz,2H,NHCH2CH2),3.77(q,J=7.0Hz,4H,SiOCH2CH3),6,29(br s,1H,NH)
13
C NMR(101 MHz,CDCl3) d. -4.99,11.24,18.36,22.65,43.61,58.26,166.89,169.66,170.85
EI-MS(70 eV) m/z 352(M+)
元素分析(實測值/計算值) C:37.3/37.49,H:5.6/5.72,N:39.8/39.74
[合成例A-6]
於-10℃下,將10.0g(0.054mol)的三聚氰氯,加入100ml的THF溶液。然後,置於氮氣氣氛下。對該三聚氰氯溶液,滴入含有12.8g(0.054mol)的4-胺基丁基三乙氧基矽烷與7.7g(0.075mol)的三乙胺的THF溶液60ml。結束滴入後,持續進行攪拌2小時。反應結束之後,去除產生的三乙胺鹽酸鹽。於減壓下(20mmHg)餾除THF,得到粗生成物。藉由矽膠管柱層析儀進行純化。所得純化物係油狀。其量為17.1g(產率:83.0%)。
將所得純化物(化合物)的鑑定,係以元素分析測定裝置、NMR測定裝置及MS測定裝置進行。結果,確定純化物為6-(4-三乙氧基矽基丁基)胺基-1,3,5-三嗪-2,4-二氯化物(TEB-DC)。
TEB-DC
1
H NMR(400MHz,CDCl3
)d 0.65(t,J=8.0Hz,2H,CH2CH2Si),1.22(t,J=7.0Hz,9H,SiOCH2CH3),1.50(quint,J=8.0Hz,2H,CH2CH2Si),1.71(quint,J=8.0Hz,2H,NHCH2CH2CH2),3.50(q,J=8.0Hz,2H,NHCH2CH2),3.82(q,J=7.0Hz,6H,SiOCH2CH3),6.70(br s,1H,NH)
13
C NMR(101MHz,CDCl3)d 9.98,18.25,20.06,31.92,41.16,58.34,165.76,169.56,170.90
EI-MS(70eV)m/z 383(M+)
元素分析(實測值/計算值)C:40.6/40.73,H:6.3/6.31,N:14.6/16.62
將上述TEB-DC15.0g(0.039mol),於50~60℃下,加入甲醇100ml。置於氮氣氣氛下。對該TEB-DC溶液,邊攪拌滴入含有5.6g(0.086mol)的NaN3
之甲醇50ml。結束滴入
後,持續進行攪拌3小時。於減壓下(20mmHg)係餾除甲醇,得到粗生成物。對該粗生成物加入醚200ml。去除生成之鹽及過剩量的NaN3
被。藉由矽膠管柱層析儀進行純化。所得純化物係白色粉體。其量為14.0g(產率:97.2%)。
將所得純化物(化合物)的鑑定,係以元素分析測定裝置、NMR測定裝置及MS測定裝置進行。結果,確定純化物為6-(4-三乙氧基矽基丁基)胺基-1,3,5-三嗪-2,4-二疊氮(TEB-DAZ)。
TEB-DAZ
1
H NMR(400MHz,CDCl3
)d 0.66(t,J=8.0Hz,2H,CH2CH2Si),1.22(t,J=7.0Hz,9H,SiOCH2CH3),1.50(quint,J=8.0Hz,2H,CH2CH2Si),1.65(quint,J=8.0Hz,2H,NHCH2CH2CH2),3.45(q,J=8.0Hz,2H,NHCH2CH2),3.81(q,J=7.0Hz,6H,SiOCH2CH3),6.06(br s,1H,NH)
13
C NMR(101MHz,CDCl3)d.10.03,18.27,20.10,31.23,40.74,58.39,165.90,169.63,170.43
EI-MS(70eV)m/z 396(M+)
元素分析(實測值/計算值)C:39.4/39.38,H:6.0/6.10,N:35.2/35.33
依照上述實施例4進行。惟,取代TE-DAZ使用TEU-DAZ、DEM-DAZ、TEB-DAZ、TE-ASH。使用之基板,係ABS樹脂製基板、PP樹脂製基板、FKM基板、Q基板。
對上述步驟Y(鍍敷步驟)之處理前,於上述步驟W(紫外線照射步驟)之處理後,進行XPS分析(X射線光電子光譜分析裝置:ULVACPHI公司製之上述裝置),將結果示於表-5。
調查所得30μm厚之Cu鍍敷膜之密著強度,將其結果示於表-6。亦進行熱衝擊試驗,將其結果示於表-6。密著強度及熱衝擊試驗的內容與上述密著強度及熱衝擊試驗內容相同。
根據此,可知藉由本實施例之Cu鍍敷膜懂密著強度優良。
本申請係以2010年10月4日申請之日本申請特願2010-225165為基礎主張優先權,將其全部內容包含於此。
圖1係TE-DAZ之1
H-NMR的光譜圖。
圖2係TE-DAZ之13
C-NMR的光譜圖。
Claims (29)
- 一種金屬膜形成方法,包含:於基體表面設置包含下述化合物(α)之劑之步驟(X);及於上述化合物(α)的表面,藉由濕式鍍敷的手法,設置金屬膜的步驟(Y),其特徵在於:上述化合物(α)係於一分子內,具有OH基或OH生成基、及疊氮基、與三嗪環之化合物,上述基體係使用聚合物構成而成。
- 如申請專利範圍第1項所述的金屬膜形成方法,其中進一步具備:於上述步驟(X)之後,且在於上述步驟(Y)之前,對存在於上述基體表面之上述化合物(α)照射既定圖案的光的步驟(W)。
- 如申請專利範圍第2項所述的金屬膜形成方法,其中藉由上述步驟(W)的光照射,使上述基體與上述化合物(α)的疊氮基進行化學反應,使上述化合物(α)與上述基體表面鍵結。
- 如申請專利範圍第2項所述的金屬膜形成方法,其中上述光係紫外線。
- 如申請專利範圍第1項所述的金屬膜形成方法,其中上述OH基或OH生成基,係烷氧基矽基(亦包含上述烷氧基為OH基之情形)。
- 如申請專利範圍第1項所述的金屬膜形成方法,其 中上述化合物(α)係以下述通式[I]所示的化合物:
- 如申請專利範圍第1項所述的金屬膜形成方法,其中上述化合物(α)係以下述通式[Io]所示的化合物:
- 如申請專利範圍第1項所述的金屬膜形成方法,其中上述化合物(α)係以下述通式[Ia]所示的化合物:通式[Ia]
- 如申請專利範圍第1項所述的金屬膜形成方法,其中上述化合物(α)係以下述通式[Ib]所示的化合物:
- 如申請專利範圍第1項所述的金屬膜形成方法,其中進一步於上述步驟(X)之後,且於上述步驟(Y)之前,於上述化合物(α)的表面,設置以下述式[II]所示之物質之步驟(V):
- 如申請專利範圍第1項所述的金屬膜形成方法,其中進一步於上述步驟(X)之後,且於上述步驟(Y)之前,於上述化合物(α)的表面上,設置烷氧基矽基、烷氧基鋁基及/或烷氧基鈦基的化合物(β)之步驟(U)。
- 如申請專利範圍第10項所述的金屬膜形成方法,其中進一步於上述步驟(V)之後,且於上述步驟(Y)之前,於上述化合物(α)的表面上,設置烷氧基矽基、烷氧基鋁基及/或烷氧基鈦基的化合物(β)之步驟(U)。
- 如申請專利範圍第11或12項所述的金屬膜形成方法,其中上述化合物(β)係以下述通式[T]所示的化合物:通式[T]L-Si(M’)n (OM)3-n 式中,L係有機基(有機基亦可包含碳、氫以外的元素;有機基亦可包含取代基;有機基可為脂肪族、芳香族、鏈狀、環類之任何形態);M’係碳數1~4之鏈狀烴基;M係H或碳數1~4之鏈狀烴基;n係0~2之整數;上述M’與M可相同亦可不同。
- 如申請專利範圍第11或12項所述的金屬膜形成方法,其中上述化合物(β)係以下述通式[III]所示的化合物:
- 如申請專利範圍第11或12項所述的金屬膜形成方法,其中上述化合物(β)係以下述通式[IV]所示的化合物:
- 如申請專利範圍第1項所述的金屬膜形成方法,其中上述基體係配線用基板,金屬膜的一部分係至少包含Cu之鍍敷膜。
- 一種金屬膜之製品,包含:基體;設置於上述基體表面之下述化合物(α);及 設於上述化合物(α)上之濕式鍍敷金屬膜而成,其特徵在於:上述化合物(α)係於一分子內,具有OH基或OH生成基、及疊氮基、與三嗪環之化合物,上述基體係使用聚合物構成而成。
- 如申請專利範圍第17項所述的金屬膜之製品,其中上述基體與上述化合物(α)係化學鍵結而成。
- 如申請專利範圍第17項所述的金屬膜之製品,其中上述OH基或OH生成基為烷氧基矽基(亦包含上述烷氧基為OH基之情形)。
- 如申請專利範圍第17項所述的金屬膜之製品,其中上述化合物(α)係以下述通式[I]所示的化合物:
- 如申請專利範圍第17項所述的金屬膜之製品,其中上述化合物(α)係以下述通式[Io]所示的化合物:通式[Io]
- 如申請專利範圍第17項所述的金屬膜之製品,其中上述化合物(α)係以下述通式[Ia]所示的化合物:
- 如申請專利範圍第17項所述的金屬膜之製品,其中上述化合物(α)係以下述通式[Ib]所示的化合物:
- 如申請專利範圍第17項所述的金屬膜之製品,其中上述化合物(α)係以下述通式[II]所示的化合物:
- 如申請專利範圍第17項所述的金屬膜之製品,其中將具有烷氧基矽基、烷氧基鋁基及/或烷氧基鈦基的化合物(β),設於上述化合物(α)的表面。
- 如申請專利範圍第25項所述的金屬膜之製品,其中上述化合物(β)係以下述通式[T]所示的化合物:通式[T]L-Si(M’)n (OM)3-n 式中,L係有機基(有機基亦可包含碳、氫以外的元素;有機基亦可包含取代基;有機基可為脂肪族、芳香族、鏈狀、環類之任何形態);M’係碳數1~4之鏈狀烴基;M係H 或碳數1~4之鏈狀烴基;n係0~2之整數;上述M’與M可相同亦可不同。
- 如申請專利範圍第25項所述的金屬膜之製品,其中上述化合物(β)係以下述通式[III]所示的化合物:
- 如申請專利範圍第25項所述的金屬膜之製品,其中上述化合物(β)係以下述通式[IV]所示的化合物
- 如申請專利範圍第17項所述的金屬膜之製品,其係配線基板。
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