JPWO2016111036A1 - Surface treatment agent for metal substrates - Google Patents
Surface treatment agent for metal substrates Download PDFInfo
- Publication number
- JPWO2016111036A1 JPWO2016111036A1 JP2016568268A JP2016568268A JPWO2016111036A1 JP WO2016111036 A1 JPWO2016111036 A1 JP WO2016111036A1 JP 2016568268 A JP2016568268 A JP 2016568268A JP 2016568268 A JP2016568268 A JP 2016568268A JP WO2016111036 A1 JPWO2016111036 A1 JP WO2016111036A1
- Authority
- JP
- Japan
- Prior art keywords
- ink
- metal substrate
- acid
- surface treatment
- coating film
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 62
- 239000002184 metal Substances 0.000 title claims abstract description 62
- 239000000758 substrate Substances 0.000 title claims abstract description 54
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002280 amphoteric surfactant Substances 0.000 claims abstract description 13
- 238000005530 etching Methods 0.000 claims description 26
- 229910000679 solder Inorganic materials 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 abstract description 17
- 230000000740 bleeding effect Effects 0.000 abstract description 12
- -1 alkylammonium hydride Chemical class 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 238000009736 wetting Methods 0.000 description 12
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 8
- 229960003237 betaine Drugs 0.000 description 8
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 238000013461 design Methods 0.000 description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
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- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- IFDUTQGPGFEDHJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolan-2-one Chemical compound CC(=C)C(O)=O.O=C1CCCO1 IFDUTQGPGFEDHJ-UHFFFAOYSA-N 0.000 description 2
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
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- 239000001384 succinic acid Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- DCNHQNGFLVPROM-QXMHVHEDSA-N (z)-n,n-dimethyloctadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(C)C DCNHQNGFLVPROM-QXMHVHEDSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- VDWRUZRMNKZIAJ-UHFFFAOYSA-N tetradecylazanium;acetate Chemical compound CC(O)=O.CCCCCCCCCCCCCCN VDWRUZRMNKZIAJ-UHFFFAOYSA-N 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229950004616 tribromoethanol Drugs 0.000 description 1
- DWWMSEANWMWMCB-UHFFFAOYSA-N tribromomethylsulfonylbenzene Chemical compound BrC(Br)(Br)S(=O)(=O)C1=CC=CC=C1 DWWMSEANWMWMCB-UHFFFAOYSA-N 0.000 description 1
- NNENFOSYDBTCBO-UHFFFAOYSA-M tributyl(hexadecyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC NNENFOSYDBTCBO-UHFFFAOYSA-M 0.000 description 1
- HNJXPTMEWIVQQM-UHFFFAOYSA-M triethyl(hexadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC HNJXPTMEWIVQQM-UHFFFAOYSA-M 0.000 description 1
- MBXYEKQOJQZLHR-UHFFFAOYSA-M triethyl(hexadecyl)phosphanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[P+](CC)(CC)CC MBXYEKQOJQZLHR-UHFFFAOYSA-M 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- 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
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
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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
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- Metallurgy (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
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- Ink Jet Recording Methods And Recording Media Thereof (AREA)
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Abstract
インクジェット方式を用いてパターン塗膜を形成するにあたり、滲みのない高精細なパターン塗膜を描画することが可能な、金属基材の前処理に用いられる表面処理剤、および、パターン塗膜の形成方法を提供する。金属基材上に、インキをインクジェット方式により塗工してパターン塗膜を形成するに先立って用いられる金属基材用表面処理剤である。酸と、カチオン系界面活性剤および両性界面活性剤のうちの少なくともいずれか１種と、水と、を含む組成物からなる。Surface treatment agent used for pretreatment of metal base material and pattern coating that can draw high-definition pattern coating without bleeding when forming pattern coating using inkjet method Provide a method. This is a surface treatment agent for a metal substrate that is used prior to forming a pattern coating film by coating ink on a metal substrate by an ink jet method. The composition comprises an acid, at least one of a cationic surfactant and an amphoteric surfactant, and water.
Description
本発明は、金属基材用表面処理剤（以下、単に「表面処理剤」とも称する）に関し、詳しくは、金属基材上にインキをインクジェット方式により塗工して高精細なパターン塗膜を形成するために用いられる金属基材用の表面処理剤およびこれを用いたパターン塗膜の形成方法に関する。 The present invention relates to a surface treatment agent for metal substrates (hereinafter, also simply referred to as “surface treatment agent”). Specifically, ink is applied on a metal substrate by an ink jet method to form a high-definition pattern coating film. The present invention relates to a surface treatment agent for a metal substrate used for the purpose and a method for forming a pattern coating film using the same.
一般に、金属のパターンは、銅板などの金属基材上にエッチングレジストパターンを形成し、不要部分をエッチングにて除去することにより得られる。例えば、プリント配線板の銅回路は、銅張りの基材上に所望のパターンのエッチングレジストを形成し、エッチングすることにより得られる。さらに、プリント配線板のソルダーレジストは、回路の保護やはんだブリッジ防止のために、銅回路上に形成される。 Generally, a metal pattern is obtained by forming an etching resist pattern on a metal substrate such as a copper plate and removing unnecessary portions by etching. For example, a copper circuit of a printed wiring board can be obtained by forming an etching resist having a desired pattern on a copper-clad base material and etching it. Furthermore, the solder resist of the printed wiring board is formed on the copper circuit for circuit protection and solder bridge prevention.
エッチングレジストやソルダーレジストは、一般に、スクリーン版などを用いた印刷法や、露光および現像工程を行うフォトリソグラフィー法により形成される。また、小ロット生産への対応が可能であって、版やフォトマスクなどが省けることから、インクジェット方式によりエッチングレジストやソルダーレジストをパターン描画する方法も提案されている。 The etching resist and the solder resist are generally formed by a printing method using a screen plate or the like, or a photolithography method in which exposure and development processes are performed. In addition, a method of drawing an etching resist or a solder resist by an ink jet method has been proposed because it can cope with a small lot production and omits a plate or a photomask.
例えば、特許文献１では、エッチングレジストをインクジェット方式で描画する方法が、特許文献２では、ソルダーレジストをインクジェット方式で描画する方法が、それぞれ提案されている。しかし、インクジェット方式に適用できるレジストインキの粘度は非常に低く、銅の表面のような吸収性のない基材に塗布すると、滲みが発生してしまう。 For example, Patent Document 1 proposes a method of drawing an etching resist by an ink jet method, and Patent Document 2 proposes a method of drawing a solder resist by an ink jet method. However, the viscosity of resist ink that can be applied to the ink jet system is very low, and bleeding occurs when applied to a non-absorbing substrate such as a copper surface.
そこで、例えば、特許文献３では、基材を加熱または冷却して、インキによる印字後にインキの粘度を高める方法が、特許文献４では、凸版反転印刷法で隔壁を形成しその内側にインクジェット方式によりインキを注入する方法が、それぞれ提案されている。また、特許文献５のように、紫外線硬化型のインキを用いて、噴射ノズルの近傍に紫外線照射手段を設けた装置も提案されている。この技術は、塗布後のインキを短時間で硬化させることにより、にじみを少なくすることができるものであり、プリント配線板用として使用されている。 Therefore, for example, in Patent Document 3, the method of heating or cooling the base material to increase the viscosity of the ink after printing with ink is used. In Patent Document 4, a partition is formed by a letterpress reverse printing method, and an ink jet system is formed on the inside thereof. Each method of injecting ink has been proposed. Further, as in Patent Document 5, an apparatus in which an ultraviolet irradiation means is provided in the vicinity of a jet nozzle using an ultraviolet curable ink has been proposed. This technique can reduce bleeding by curing the ink after application in a short time, and is used for printed wiring boards.
インクジェット方式を用いてインキを塗布するにあたり、被塗布物が金属表面のような吸収性を有しない基材である場合には、上述したように、特許文献５に記載されているような装置を用いれば、滲みを少なくすることが可能である。 When applying the ink using the inkjet method, if the object to be coated is a base material that does not have an absorptivity such as a metal surface, an apparatus as described in Patent Document 5 is used as described above. If used, it is possible to reduce bleeding.
しかしながら、その効果は充分なものではなく、結果的には満足できるような高精細なパターン塗膜は得られず、従来の、スクリーン版などを用いる印刷法や露光および現像工程を行うフォトリソグラフィー法と比較して、描画品質的に劣ったものしか得られていなかった。特に、マーキングインキの場合、この問題が顕著であった。 However, the effect is not sufficient, and as a result, a satisfactory high-definition pattern coating film cannot be obtained, and a conventional photolithography method using a printing method using a screen plate or the like and an exposure and development process. Compared to the above, only the inferior drawing quality was obtained. In particular, in the case of marking ink, this problem was remarkable.
そこで、本発明の目的は、インクジェット方式を用いてパターン塗膜を形成するにあたり、滲みのない高精細なパターン塗膜を描画することが可能な、金属基材の前処理に用いられる表面処理剤、および、パターン塗膜の形成方法を提供することにある。 Accordingly, an object of the present invention is to provide a surface treatment agent used for pretreatment of a metal substrate, capable of drawing a high-definition pattern coating film without bleeding when forming a pattern coating film using an inkjet method. And it is providing the formation method of a pattern coating film.
本発明者らは、上記課題を解決するために鋭意検討した結果、酸と、カチオン系界面活性剤および両性界面活性剤のうちの少なくともいずれか１種と、水と、を含む組成物からなる表面処理剤を用いることにより、上記課題を解決できることを見出して、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors comprise a composition containing an acid, at least one of a cationic surfactant and an amphoteric surfactant, and water. The inventors have found that the above problems can be solved by using a surface treating agent, and have completed the present invention.
すなわち、本発明の金属基材用表面処理剤は、金属基材上に、インキをインクジェット方式により塗工してパターン塗膜を形成するに先立って用いられる金属基材用表面処理剤であって、酸と、カチオン系界面活性剤および両性界面活性剤のうちの少なくともいずれか１種と、水と、を含む組成物からなることを特徴とするものである。 That is, the surface treatment agent for a metal substrate of the present invention is a surface treatment agent for a metal substrate that is used prior to forming a pattern coating film by coating ink on a metal substrate by an ink jet method. And an acid, at least one of a cationic surfactant and an amphoteric surfactant, and water.
また、本発明のパターン塗膜の形成方法は、上記本発明の金属基材用表面処理剤により表面処理した金属基材上に、インキをインクジェット方式により塗工してパターン塗膜を形成することを特徴とするものである。 Moreover, the formation method of the pattern coating film of this invention forms the pattern coating film by coating ink with the inkjet system on the metal base material surface-treated with the surface treating agent for metal base materials of the said invention. It is characterized by.
本発明の金属基材用表面処理剤によれば、インクジェット方式を用いてパターン塗膜を形成するにあたり、滲みのない高精細なパターン塗膜を描画することが可能となる。また、エッチングレジストを介した金属基材のエッチング処理にて回路を形成する場合、エッチングレジストを金属基材から剥離する必要があるが、本発明の金属基材用表面処理剤によれば、この剥離時間を短縮できる効果がある。 According to the surface treatment agent for a metal substrate of the present invention, it is possible to draw a high-definition pattern coating without bleeding when forming a pattern coating using an inkjet method. In addition, when forming a circuit by etching a metal substrate through an etching resist, it is necessary to peel the etching resist from the metal substrate. According to the surface treatment agent for a metal substrate of the present invention, There is an effect that the peeling time can be shortened.
以下、本発明の実施の形態を、詳細に説明する。
本発明の金属基材用表面処理剤は、金属基材上に、インキをインクジェット方式により塗工してパターン塗膜を形成するに先立って、前処理に用いられるものであり、酸と、カチオン系界面活性剤および両性界面活性剤のうちの少なくともいずれか１種と、水と、を含む組成物からなる点が重要である。Hereinafter, embodiments of the present invention will be described in detail.
The surface treatment agent for a metal substrate according to the present invention is used for pretreatment prior to forming a pattern coating film by coating ink on a metal substrate by an ink jet method. The point which consists of a composition containing at least any one of a system surfactant and an amphoteric surfactant and water is important.
前述したように、吸収性を有しない銅などの金属基材に対し、インクジェット方式でインキの塗工を行った場合、従来の方法では、滲みを十分に抑制して高品質の高精細パターンを得ることはできなかった。本発明者らは鋭意検討した結果、その原因が、インキの表面エネルギーに比べて、金属基材の表面エネルギーが大きすぎる点にあることを見出した。本発明者らはさらに検討した結果、金属基材に対し、特定の組成物を用いて前処理を行うことにより、その表面エネルギー、すなわち表面張力を調整することができ、これによりインクジェット方式でインキを塗工した場合において、滲みのない高精細なパターン塗膜を描画することが可能となることを見出したものである。また、本発明の表面処理剤により前処理を行うことで、エッチングレジストが金属基材から剥離しやすくなり、剥離時間を短縮できる効果も得ることができる。本発明の表面処理剤として用いられる組成物は、高濃度の界面活性剤と酸とを配合して貯蔵や運搬を行うことが可能であり、水で希釈することで適切な濃度で使用することができる。また、水を用いることにより、酸と界面活性剤とを混合することが容易となる。 As described above, when ink is applied to a metal substrate such as copper having no absorbability by the ink jet method, the conventional method sufficiently suppresses bleeding and produces a high-quality high-definition pattern. Couldn't get. As a result of intensive studies, the present inventors have found that the cause is that the surface energy of the metal substrate is too large compared to the surface energy of the ink. As a result of further investigation, the inventors of the present invention can adjust the surface energy, that is, the surface tension, by pre-treating a metal base material with a specific composition, and thereby the ink can be ink-jetted. The present inventors have found that it is possible to draw a high-definition pattern coating film that does not bleed when the coating is applied. In addition, by performing the pretreatment with the surface treating agent of the present invention, the etching resist can be easily peeled off from the metal substrate, and the effect of shortening the peeling time can be obtained. The composition used as the surface treatment agent of the present invention can be stored and transported by mixing a high concentration surfactant and acid, and should be used at an appropriate concentration by diluting with water. Can do. Moreover, it becomes easy to mix an acid and surfactant by using water.
（酸）
本発明の表面処理剤には、酸を用いる。用いる酸としては、公知慣用の酸を用いることができ、例えば、酢酸、蟻酸、クエン酸、アスコルビン酸、メタンスルホン酸、硫酸、塩酸、リン酸、コハク酸等が挙げられる。(acid)
An acid is used for the surface treating agent of the present invention. As the acid to be used, known and commonly used acids can be used, and examples include acetic acid, formic acid, citric acid, ascorbic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid, phosphoric acid, succinic acid and the like.
（カチオン系界面活性剤および両性界面活性剤のうちの少なくともいずれか１種）
本発明の表面処理剤に用いる界面活性剤としては、カチオン系界面活性剤および両性界面活性剤のうちの少なくともいずれか１種を用いる。(At least one of cationic surfactants and amphoteric surfactants)
As the surfactant used in the surface treatment agent of the present invention, at least one of a cationic surfactant and an amphoteric surfactant is used.
カチオン系界面活性剤とは、水中で解離して陽イオンとなる官能基を有する界面活性剤である。カチオン系界面活性剤としては、テトラデシルアミン酢酸塩、オクタデシルアミン酢酸塩、ラウリルトリメチルアンモニウムクロライド、セチルトリメチルアンモニウムクロライド、ジオクチルジメチルアンモニウムクロライド、ドデシルトリメチルアンモニウムクロライド、ヤシアルキルトリメチルアンモニウムクロライド、ヘキサデシルトリメチルアンモニウムクロライド、牛脂アルキルトリメチル−アンモニウムクロライド、オクタデシルトリメチルアンモニウムクロライド、ベヘニルトリメチルアンモニウムクロライド、ジデシルジメチルアンモニウムクロライド、ジ硬化牛脂アルキルジメチルアンモニウムクロライド、ジオレイルジメチルアンモニウムクロライド、ヤシアルキルジメチルベンジルアンモニウムクロライド、テトラデシルジメチルベンジルアンモニウムクロライド、Ｎ，Ｎ−ジアシルオキシエチル−Ｎ−ヒドロキシエチル−Ｎ−メチルアンモニウムメチルサルフェート、１−メチル−１−ヒドロキシエチル−２−牛脂アルキルイミダゾニウムクロライド、アルキルアンモニウムハイドライド、ベンジルトリエチルアンモニウムブロマイド、ベンジルトリメチルアンモニウムクロライド、ヘキサデシルトリエチルアンモニウムブロマイド、オクチルトリエチルアンモニウムブロマイド、テトラ−ｎ−ブチルアンモニウムブロマイド、テトラ−ｎ−ブチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、トリオクチルメチルアンモニウムクロライド、ヘキサデシルトリエチルホスホニウムブロマイド、ヘキサデシルトリブチルホスホニウムクロライド、テトラ−ｎ−ブチルホスホニウムブロマイド、テトラ−ｎ−ブチルホスホニウムクロライド、トリオクチルエチルホスホニウムブロマイドおよびテトラフェニルホスホニウムブロマイド等が挙げられる。 A cationic surfactant is a surfactant having a functional group that dissociates in water and becomes a cation. Cationic surfactants include tetradecylamine acetate, octadecylamine acetate, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, dioctyldimethylammonium chloride, dodecyltrimethylammonium chloride, cocoalkyltrimethylammonium chloride, hexadecyltrimethylammonium chloride. Tallow alkyltrimethyl-ammonium chloride, octadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, didecyldimethylammonium chloride, di-cured tallow alkyldimethylammonium chloride, dioleyldimethylammonium chloride, coconut alkyldimethylbenzylammonium chloride, tetra Sildimethylbenzylammonium chloride, N, N-diacyloxyethyl-N-hydroxyethyl-N-methylammonium methyl sulfate, 1-methyl-1-hydroxyethyl-2-tallow alkylimidazolium chloride, alkylammonium hydride, benzyltriethylammonium Bromide, benzyltrimethylammonium chloride, hexadecyltriethylammonium bromide, octyltriethylammonium bromide, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetraethylammonium chloride, trioctylmethylammonium chloride, hexadecyltriethylphosphonium bromide, Hexadecyltributylphosphonium Chloride, tetra -n- butyl phosphonium bromide, tetra -n- butyl phosphonium chloride, tri-octyl ethyl phosphonium bromide and tetraphenylphosphonium bromide, and the like.
両性界面活性剤とは、分子中にカチオン性部位とアニオン性部位とを有する界面活性剤であり、水中で、アルカリ性領域では陰イオン界面活性剤の性質を、酸性領域では陽イオン界面活性剤の性質を示す界面活性剤である。両性界面活性剤としては、ヤシ油ジメチルベタイン、ヤシ油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、パーム核油脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン、ラウリルジメチルアミノ酢酸ベタイン、ステアリルジメチルアミノ酢酸ベタイン、ラウリン酸アミドプロピルジメチルアミノ酢酸ベタイン、ドデシルアミノメチルジメチルスルホプロピルベタイン、オクタデシルアミノメチルジメチルスルホプロピルベタイン、コカミドプロピルヒドロキシスルタイン、２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチル−イミダゾリウムベタイン、ラウリルアミノジ酢酸モノナトリウム、ラウリルジアミノエチルグリシンナトリウム、ラウロイルメチルアラニンナトリウム、ラウロイルグルタミン酸ナトリウム、ラウロイルグルタミン酸カリウム、ラウロイルメチル−β−アラニン、ラウリルジメチルアミンＮ−オキシド、オレイルジメチルアミンＮ−オキシド等が挙げられる。 An amphoteric surfactant is a surfactant having a cationic site and an anionic site in the molecule. In water, the properties of an anionic surfactant in the alkaline region and the cationic surfactant in the acidic region. It is a surfactant that exhibits properties. Amphoteric surfactants include coconut oil dimethyl betaine, palm oil fatty acid amidopropyl dimethylaminoacetic acid betaine, palm kernel fatty acid amidopropyl dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, stearyl dimethylaminoacetic acid betaine, lauric acid amidopropyldimethyl. Betaine aminoacetate, dodecylaminomethyldimethylsulfopropylbetaine, octadecylaminomethyldimethylsulfopropylbetaine, cocamidopropylhydroxysultain, 2-alkyl-N-carboxymethyl-N-hydroxyethyl-imidazolium betaine, laurylaminodiacetic acid mono Sodium, sodium lauryldiaminoethylglycine, sodium lauroylmethylalanine, sodium lauroylglutamate, Potassium yl glutamate, lauroyl methyl -β- alanine, lauryl dimethylamine N- oxide, oleyl dimethylamine N- oxides and the like.
本発明の表面処理剤として用いられる組成物において、上記酸と上記界面活性剤との質量比率は、好適には１００：０．１〜１００：５０とすることができ、より好適には１００：０．２〜１００：２０である。各成分の比率を上記範囲とすることで、滲みのない高精細なパターン塗膜をより確実に得ることができるものとなる。一方、水の配合量は、最小量は各種酸が溶ける量であればよく、最大量は界面活性剤の濃度が０．０００１質量％以下にならない量とすることができ、より好適には、界面活性剤の濃度が０．００１〜０．１質量％となる量である。 In the composition used as the surface treating agent of the present invention, the mass ratio of the acid to the surfactant can be preferably 100: 0.1 to 100: 50, and more preferably 100: 0.2 to 100: 20. By setting the ratio of each component in the above range, a high-definition pattern coating without bleeding can be obtained more reliably. On the other hand, the blending amount of water may be a minimum amount that can dissolve various acids, and the maximum amount can be an amount in which the concentration of the surfactant does not become 0.0001% by mass or less. The amount of the surfactant is 0.001 to 0.1% by mass.
本発明の表面処理剤による金属基材の処理は、上記表面処理剤を、そのままか、または、任意の濃度で水や各種水溶性溶剤で希釈した状態で、金属基材の表面に塗布するかまたは浸漬して、必要に応じて洗浄し、乾燥させることにより行うことができる。 In the treatment of the metal substrate with the surface treatment agent of the present invention, the surface treatment agent is applied to the surface of the metal substrate as it is or diluted with water or various water-soluble solvents at an arbitrary concentration. Or it can carry out by immersing, washing | cleaning as needed, and making it dry.
（金属基材）
金属基材としては、プリント配線板に通常使用される銅、鉄、錫、アルミニウム、銀、ステンレス、真鍮、ニッケル、チタン、および、それらの合金などの金属箔が挙げられる。本発明は、特には、プリント配線板上に配設された金属基材としての銅箔上に、インキをインクジェット方式により塗工して、プリント配線板用レジストインキの塗膜を形成する際に有用である。中でも、エッチングレジストインキやソルダーレジストインキの塗膜を形成する際に特に有用である。(Metal base material)
Examples of the metal substrate include metal foils such as copper, iron, tin, aluminum, silver, stainless steel, brass, nickel, titanium, and alloys thereof that are usually used for printed wiring boards. The present invention is particularly suitable for forming a coating film of a resist ink for printed wiring board by applying ink by an ink jet method on a copper foil as a metal substrate disposed on the printed wiring board. Useful. Among them, it is particularly useful when forming a coating film of etching resist ink or solder resist ink.
エッチングレジストインキを塗布する基材は、絶縁性のシートに、金属基材としての、銅などの金属箔を形成したものである。絶縁性のシートは、一般的には、ガラスクロス、不織布、紙等にエポキシ樹脂、フェノール樹脂を含浸させ硬化させたものであるが、用途に応じて含浸させていないものも選択できる。例えば、エポキシ樹脂、メラミン樹脂、フェノール樹脂、尿素樹脂、不飽和ポリエステル樹脂、ポリイミド等の熱硬化樹脂、ポリエチレン、ポリプロピレン、ポリスチレン、ＡＢＳ樹脂、塩化ビニル樹脂、メタクリル酸メチル樹脂、ナイロン、ポリエステル樹脂、フッ素樹脂、ポリカーボネート、ポリアセタール、ポリアミド、ポリフェニレンエーテル、非晶ポリアリレート、ポリサルフォン、ポリエーテルサルフォン、ポリフェニレンスルファイド、ポリエーテルエーテルケトン、熱可塑性ポリイミド、ポリエーテルイミド、液晶ポリマー等の熱可塑性樹脂、窒化ケイ素焼結体、サイアロン焼結体、炭化ケイ素焼結体、アルミナ焼結体、窒化アルミニウム焼結体等のセラミックを好適に使用することができる。このようなシート上への金属箔の形成方法としては、単体の金属箔を熱融着や接着剤を用いて張り付ける方法、シード層をつけてめっき法にて形成する方法、蒸着法にて形成する方法等があり、それらを組み合わせて形成してもよい。 The substrate on which the etching resist ink is applied is obtained by forming a metal foil such as copper as a metal substrate on an insulating sheet. The insulating sheet is generally a glass cloth, non-woven fabric, paper, or the like impregnated with an epoxy resin or a phenol resin and cured, but a sheet that is not impregnated can be selected depending on the application. For example, epoxy resin, melamine resin, phenol resin, urea resin, unsaturated polyester resin, thermosetting resin such as polyimide, polyethylene, polypropylene, polystyrene, ABS resin, vinyl chloride resin, methyl methacrylate resin, nylon, polyester resin, fluorine Resin, polycarbonate, polyacetal, polyamide, polyphenylene ether, amorphous polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, thermoplastic polyimide, polyetherimide, liquid crystal polymer and other thermoplastic resins, silicon nitride Ceramics such as a sintered body, a sialon sintered body, a silicon carbide sintered body, an alumina sintered body, and an aluminum nitride sintered body can be suitably used. As a method of forming a metal foil on such a sheet, a method of attaching a single metal foil using heat fusion or an adhesive, a method of forming a seed layer by plating, and a vapor deposition method There are methods for forming them, and they may be formed in combination.
ソルダーレジストインキを塗布する基材は、エッチングレジストインキに使用したものと同様の基材が使用でき、絶縁性のシートに金属基材としての、銅などの金属箔を形成したものに、エッチングレジストインキを塗布してエッチング法により回路パターンを形成したものや、金属ペーストなどで直接回路パターンを印刷したものなどが使用できる。 The same base material as that used for the etching resist ink can be used as the base material to which the solder resist ink is applied, and the etching resist is formed by forming a metal foil such as copper on the insulating sheet as a metal base material. A circuit pattern formed by applying an ink and an etching method or a circuit pattern printed directly with a metal paste or the like can be used.
本発明のパターン塗膜の形成方法においては、上記表面処理剤により表面処理した金属基材上に、インキをインクジェット方式により塗工してパターン塗膜を形成する。 In the method for forming a patterned coating film of the present invention, a pattern coating film is formed by coating ink on the metal substrate surface-treated with the surface treatment agent by an inkjet method.
前述したように、本発明においては、かかる金属基材に上記表面処理剤を用いて表面処理を施すことで、金属基材の表面張力を調整することができる。具体的には、本発明においては、金属基材に対し表面処理を施すことで、その表面張力を低下させることができる。なお、通常、被塗布物である金属基材は、塗布するインキよりも高い表面エネルギー（表面張力）でなければならない。これは、被塗布物である金属基材が、塗布するインキよりも低い表面エネルギー（表面張力）を有すると、はじきや未着が激しく発生して、塗膜として成り立たなくなるからである。しかし、即硬化型のインクジェットにおいては、常識を覆し、金属基材の表面エネルギーが塗布するインキよりもある程度低い値であっても、良好な結果となることが判った。 As described above, in the present invention, the surface tension of the metal substrate can be adjusted by subjecting the metal substrate to a surface treatment using the surface treatment agent. Specifically, in the present invention, the surface tension can be reduced by performing a surface treatment on the metal substrate. In general, a metal substrate that is an object to be coated must have a higher surface energy (surface tension) than the ink to be coated. This is because if the metal base material to be coated has a surface energy (surface tension) lower than that of the ink to be coated, repelling and non-sticking occur vigorously and the coating film cannot be formed. However, in the quick-curing type ink jet, it has been found that good results are obtained even if the surface energy of the metal substrate is somewhat lower than that of the applied ink.
本発明においては、具体的には例えば、金属基材の濡れ指数とインキの表面張力との差を、＋２以下とすることができ、好適には−１３以上＋２以下、より好適には−１２以上＋２以下とする。ここで、本発明において、金属基材の濡れ指数とインキの表面張力との差とは、金属基材の濡れ指数（表面張力（単位：ｍＮ／ｍ）と同値）から、インキの表面張力（単位：ｍＮ／ｍ）を引いた値である。金属基材の濡れ指数とインキの表面張力との差が＋２以下であると、ラインおよび文字共により鮮明になる点で好ましい。なお、金属基材の表面張力を調整するのは、一般に、金属基材の表面張力はインキと比較して大きすぎるため、インキの表面張力を調整して金属基材に近づけることは困難であるためである。なお、金属基材に対する表面処理の具体的な方法としては、本発明の上記表面処理剤を用いる他、例えば、金属基材の表面に、金属表面調整剤を塗布する方法が挙げられる。 In the present invention, specifically, for example, the difference between the wetting index of the metal substrate and the surface tension of the ink can be +2 or less, preferably −13 or more and +2 or less, more preferably −12. Above +2 Here, in the present invention, the difference between the wetting index of the metal substrate and the surface tension of the ink is the surface tension of the ink (the same value as the surface tension (unit: mN / m)) of the metal substrate. (Unit: mN / m). It is preferable that the difference between the wetting index of the metal substrate and the surface tension of the ink is +2 or less because both the line and the characters become clearer. The surface tension of the metal substrate is generally adjusted because the surface tension of the metal substrate is too large compared to the ink, so it is difficult to adjust the surface tension of the ink and bring it closer to the metal substrate. Because. In addition, as a specific method of the surface treatment for the metal substrate, in addition to using the surface treatment agent of the present invention, for example, a method of applying a metal surface conditioner to the surface of the metal substrate can be mentioned.
（インキ）
本発明に用いられるインキとしては、ソルダーレジストインキおよびエッチングレジストインキの少なくともいずれか１種を用いることができる。(ink)
As the ink used in the present invention, at least one of solder resist ink and etching resist ink can be used.
エッチングレジストインキとしては、インクジェット方式で塗布可能な程度の低粘度であって、エッチング後に剥離可能な組成物であれば使用できるが、塗布後に紫外線により硬化し、アルカリ水溶液にて剥離可能な組成物が望ましい。このような組成物は、カルボキシル基含有モノマー、単官能モノマー、多官能モノマー、光重合開始剤、および、その他任意成分の組み合わせで製造できる。 As the etching resist ink, any composition can be used as long as it has a low viscosity that can be applied by an ink jet method and can be peeled off after etching. Is desirable. Such a composition can be produced by a combination of a carboxyl group-containing monomer, a monofunctional monomer, a polyfunctional monomer, a photopolymerization initiator, and other optional components.
カルボキシル基含有モノマーとしては、酸変性エポキシ（メタ）アクリレート、（メタ）アクリル酸、（メタ）アクリル酸ダイマー、クロトン酸、α−クロルアクリル酸、ケイ皮酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸、β−カルボキシエチル（メタ）アクリレート、ω−カルボキシポリカプロラクトンモノ（メタ）アクリレート、コハク酸モノ［２−（メタ）アクリロイルオキシエチル］、マレイン酸モノ［２−（メタ）アクリロイルオキシエチル］、２−アクリロイルオキシエチルサクシネート、無水フタル酸とヒドロキシエチル（メタ）アクリレートとの反応物、無水ヘキサヒドロフタル酸とヒドロキシエチル（メタ）アクリレートとの反応物などが挙げられる。 Examples of the carboxyl group-containing monomer include acid-modified epoxy (meth) acrylate, (meth) acrylic acid, (meth) acrylic acid dimer, crotonic acid, α-chloroacrylic acid, cinnamic acid, maleic acid, fumaric acid, itaconic acid, Citraconic acid, mesaconic acid, β-carboxyethyl (meth) acrylate, ω-carboxypolycaprolactone mono (meth) acrylate, succinic acid mono [2- (meth) acryloyloxyethyl], mono [2- (meth) acryloyl maleate Oxyethyl], 2-acryloyloxyethyl succinate, a reaction product of phthalic anhydride and hydroxyethyl (meth) acrylate, a reaction product of hexahydrophthalic anhydride and hydroxyethyl (meth) acrylate, and the like.
単官能モノマーとしては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、グリシジルメタクリレート、γ−ブチロラクトンアクリレート、γ−ブチロラクトンメタクリレート等の（メタ）アクリレート類や、アクリロイルモルホリンなどが挙げられる。 Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , (Meth) acrylates such as hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycidyl methacrylate, γ-butyrolactone acrylate, γ-butyrolactone methacrylate, and acryloylmorpholine.
多官能モノマーとしては、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート等のポリエチレングリコールジアクリレート、あるいは、ポリウレタンジアクリレート類およびそれ等に対応するメタアクリレート類、ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレート、トリメチロールメタントリアクリレート、エチレンオキシド変性トリメチロールプロパントリアクリレート、プロピレンオキシド変性トリメチロールプロパントリアクリレート、エピクロルヒドリン変性トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、テトラメチロールメタンテトラアクリレート、エチレンオキシド変性リン酸トリアクリレート、エピクロルヒドリン変性グリセロールトリアクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールモノヒドロキシペンタアクリレート、ビスフェノールフルオレンジヒドロキシアクリレート、ビスフェノールフルオレンジメタクリレートなどが挙げられる。 Polyfunctional monomers include polyethylene glycol diacrylates such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyurethane diacrylates and corresponding methacrylates, pentaerythritol triacrylate, triethylene glycol Methylolpropane triacrylate, trimethylol methane triacrylate, ethylene oxide modified trimethylol propane triacrylate, propylene oxide modified trimethylol propane triacrylate, epichlorohydrin modified trimethylol propane triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylol methane tet Acrylate, ethylene oxide-modified phosphoric acid triacrylate, epichlorohydrin-modified glycerol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxy pentaacrylate, bisphenol fluorene dihydroxy acrylate, and bisphenol fluorene methacrylate.
光重合開始剤としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類；アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン等のアセトフェノン類；２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノプロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタン−１−オン、Ｎ，Ｎ−ジメチルアミノアセトフェノン等のアミノアセトフェノン類；２−メチルアントラキノン、２−エチルアントラキノン、２−ｔ−ブチルアントラキノン、１−クロロアントラキノン等のアントラキノン類；２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；２，４，５−トリアリールイミダゾール二量体；リボフラビンテトラブチレート；２−メルカプトベンゾイミダゾール、２−メルカプトベンゾオキサゾール、２−メルカプトベンゾチアゾール等のチオール化合物；２，４，６−トリス−ｓ−トリアジン、２，２，２−トリブロモエタノール、トリブロモメチルフェニルスルホン等の有機ハロゲン化合物；ベンゾフェノン、４，４’−ビスジエチルアミノベンゾフェノン等のベンゾフェノン類またはキサントン類；２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイドなどが挙げられる。 Examples of photopolymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2- Acetophenones such as phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( Aminoacetophenones such as 4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc. Nthraquinones; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; 2,4,5 -Triarylimidazole dimer; riboflavin tetrabutyrate; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4,6-tris-s-triazine, 2,2 Organic halogen compounds such as 1,2-tribromoethanol and tribromomethylphenylsulfone; Benzophenones such as benzophenone and 4,4′-bisdiethylaminobenzophenone or xanthones; 2,4,6- Such as trimethyl benzoyl diphenyl phosphine oxide.
ソルダーレジストインキとしては、インクジェット方式で塗布可能な程度の低粘度であって、熱や紫外線などにより硬化可能で、硬化後に耐熱性をもつ組成物であれば使用できるが、塗布後に紫外線により硬化し、その後、熱によりさらに硬化する組成物が望ましい。このような組成物は、エッチングレジストインキに使用する各種モノマーの組み合わせに加えて、エポキシ化合物やイソシアネート化合物などの硬化剤と各種任意成分を組み合わせることで製造できる。 The solder resist ink can be used as long as it has a low viscosity enough to be applied by an ink jet method and can be cured by heat or ultraviolet rays and has heat resistance after curing. Then, a composition that is further cured by heat is desirable. Such a composition can be produced by combining various optional components with a curing agent such as an epoxy compound or an isocyanate compound, in addition to a combination of various monomers used in the etching resist ink.
以下、本発明を、実施例を用いてより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
（塗布用基材の調製）
下記の表１〜３に示す配合量（質量部）で、実施例１〜１８および比較例１〜５の各高濃度液を作製し、水にて５０倍に希釈して、表面処理剤とした。基材としては、１５０×９０ｍｍの大きさのＦＲ−４銅張積層版（銅厚１８μｍ）を用いて、スクラブ研磨にて表面を粗化し、これを２３℃の各表面処理剤に６０秒間浸漬して、その後、流水にて洗浄し、乾燥させて各塗布用基材とした。なお、未処理の基材の濡れ指数は、数百〜１０００程度と考えられる。表面処理後の基材の濡れ指数を、下記の表４〜９に示す。(Preparation of coating substrate)
With the compounding amounts (parts by mass) shown in Tables 1 to 3 below, the high-concentration liquids of Examples 1 to 18 and Comparative Examples 1 to 5 were prepared, diluted 50 times with water, did. As the base material, a FR-4 copper-clad laminate (copper thickness: 18 μm) with a size of 150 × 90 mm was used to roughen the surface by scrubbing, and this was immersed in each surface treatment agent at 23 ° C. for 60 seconds. Thereafter, the substrate was washed with running water and dried to obtain each coating substrate. In addition, the wetting index of the untreated substrate is considered to be about several hundred to 1,000. Tables 4 to 9 below show the wetting indices of the base materials after the surface treatment.
ここで、濡れ指数の測定は、ＪＩＳ Ｋ６７６８に記載の方法に準拠して行い、濡れ指数３０から４２までは和光純薬工業社製のぬれ張力試験用混合液を使用し、濡れ指数２８から２９までは純水とエタノールと、場合によってはさらにフッ素系界面活性剤とを添加した混合液を使用し、ＢＹＫ−ＧＡＲＤＮＥＲ社製のダイノメーターで表面張力を測定して、調整して用いた。なお、濡れ指数の値は、表面張力（単位：ｍＮ／ｍ）と同値である。 Here, the measurement of the wetting index is performed in accordance with the method described in JIS K6768. For the wetting indices 30 to 42, a wetting tension test mixed solution manufactured by Wako Pure Chemical Industries, Ltd. is used, and the wetting indices 28 to 29 are used. Up to this point, a mixed solution to which pure water and ethanol and, in some cases, a fluorosurfactant was further added was used, and the surface tension was measured and adjusted using a dynamometer manufactured by BYK-GARDNER. Note that the value of the wetting index is the same as the surface tension (unit: mN / m).
＊２）カチオン系界面活性剤２：ジオクチルジメチルアンモニウムクロライド
＊３）両性界面活性剤１：２−アルキル−Ｎ−カルボキシメチル−Ｎ−ヒドロキシエチル−イミダゾリウムベタイン
＊４）両性界面活性剤２：ラウリルジメチルアミンＮ−オキシド
＊５）アニオン系界面活性剤１：ポリオキシエチレンアルキルフェニルエーテルフォスフェート
＊６）アニオン系界面活性剤２：アルキル硫酸エステルトリエタノールアミン
＊７）ノニオン系界面活性剤１：ポリオキシエチレンラウリルエーテル
＊８）ノニオン系界面活性剤２：ソルビタンモノオレート
（エッチングレジストインキの調製）
４−ヒドロキシブチルアクリレート２０ｇ、イソボロニルアクリレート２０ｇ、２−アクリロイルオキシエチルサクシネート３０ｇ、γ―ブチロラクトンメタクリレート１５ｇ、ペンタエリスリトールトリアクリレート５ｇ、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド５ｇ、フェニルビス（２，４，６−トリメチルベンゾイル）ホスフィンオキシド３ｇ、および、アクリル重合系レベリング剤０．３ｇを配合、撹拌して均一化し、１μｍ精度の濾過を行い、ＢＹＫ−ＧＡＲＤＮＥＲ社製のダイノメーターで測定して、表面張力３８ｍＮ／ｍのエッチングレジストインキを得た。(Preparation of etching resist ink)
4-hydroxybutyl acrylate 20 g, isobornyl acrylate 20 g, 2-acryloyloxyethyl succinate 30 g, γ-butyrolactone methacrylate 15 g, pentaerythritol triacrylate 5 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 5 g, phenylbis ( 2,4,6-trimethylbenzoyl) phosphine oxide 3 g and acrylic polymerization leveling agent 0.3 g were mixed, stirred and homogenized, filtered with 1 μm accuracy, and measured with a BYK-GARDNER dynometer. Thus, an etching resist ink having a surface tension of 38 mN / m was obtained.
（ソルダーレジストインキの調製）
トリメチロールプロパントリアクリレート３０ｇ、１，６−ヘキサンジオールジアクリレート３０ｇ、アクリル酸ブチル１０ｇ、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド５ｇ、フェニルビス（２，４，６−トリメチルベンゾイル）ホスフィンオキシド３ｇ、１，６−ヘキサメチレンジイソシアネートのトリマーをジメチルピラゾールでブロックしたブロックイソシアネート２０ｇ、および、シリコーン系レベリング剤０．０１ｇを配合、撹拌して均一化し、１μｍ精度の濾過を行い、ＢＹＫ−ＧＡＲＤＮＥＲ社製のダイノメーターで測定して、表面張力２７ｍＮ／ｍのソルダーレジストインキを得た。(Preparation of solder resist ink)
30 g of trimethylolpropane triacrylate, 30 g of 1,6-hexanediol diacrylate, 10 g of butyl acrylate, 5 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 3 g of phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide , 20 g of blocked isocyanate obtained by blocking 1,6-hexamethylene diisocyanate trimer with dimethylpyrazole, and 0.01 g of silicone leveling agent, homogenized by stirring, filtered with accuracy of 1 μm, manufactured by BYK-GARDNER As a result, a solder resist ink having a surface tension of 27 mN / m was obtained.
（インクジェット塗布）
各塗布用基材上に、上記で調製したエッチングレジストインキおよびソルダーレジストインキを用いて、富士フィルム社製のインクジェットプリンターＤｉｍａｔｉｘ Ｍａｔｅｒｉａｌｓ Ｐｒｉｎｔｅｒ ＤＭＰ−２８３１により、線幅２００μｍのラインを描画した。この際、プリントヘッドの側面にスポット型のＵＶ照射器を取り付け、描画しながら即時に硬化を行った。(Inkjet application)
A line having a line width of 200 μm was drawn on each coating substrate using the etching resist ink and the solder resist ink prepared as described above, using an inkjet printer Dimatix Materials Printer DMP-2831 manufactured by Fuji Film. At this time, a spot type UV irradiator was attached to the side surface of the print head, and curing was performed immediately while drawing.
（ライン幅の評価）
各基材について、描画されたラインの線幅を測定し、設計値との差を算出した。エッチングレジストの結果を下記の表４〜６に、ソルダーレジストの結果を下記の表７〜９に、それぞれ示す。(Evaluation of line width)
About each base material, the line width of the drawn line was measured and the difference with a design value was computed. The results of the etching resist are shown in Tables 4 to 6 below, and the results of the solder resist are shown in Tables 7 to 9 below.
（目視評価）
描画されたラインを目視にて観察し、鮮明さを評価した。ラインが鮮明で滲みが確認されないものを○、滲みが見られラインが太く見えるものを×とした。エッチングレジストの結果を下記の表４〜６に、ソルダーレジストの結果を下記の表７〜９に、それぞれ示す。(Visual evaluation)
The drawn lines were observed visually to evaluate the clarity. The case where the line was clear and no blur was observed was indicated by ○, and the case where the blur was observed and the line appeared thick was indicated by ×. The results of the etching resist are shown in Tables 4 to 6 below, and the results of the solder resist are shown in Tables 7 to 9 below.
上記表中に示す各実施例の結果から、酸と、カチオン系界面活性剤または両性界面活性剤とを併用した組成物を表面処理剤として用いることで、設計値との線幅の差が２５〜４４μｍ程度であって、滲みのない高精細なパターンが得られていることがわかる。また、実施例では、銅基材の濡れ指数とインキの表面張力との差が−１０〜＋２であって、ラインが鮮明で滲みが確認されないことがわかる。 From the results of the examples shown in the above table, the difference in line width from the design value is 25 by using a composition in which an acid and a cationic surfactant or an amphoteric surfactant are used in combination as a surface treatment agent. It can be seen that a high-definition pattern having about ~ 44 μm and no bleeding is obtained. In the examples, the difference between the wetting index of the copper base material and the surface tension of the ink is -10 to +2, and it can be seen that the lines are clear and no bleeding is observed.
これに対し、カチオン系界面活性剤を含み酸を含まない組成物を用いて前処理を行った比較例５や、酸と、カチオン系界面活性剤および両性界面活性剤以外の界面活性剤を含む組成物を用いて前処理を行った比較例１〜４では、いずれも設計値との線幅の差が１００μｍを超えており、目視で滲みが見られた。また、比較例では、いずれも銅基材の濡れ指数とインキの表面張力との差が＋３以上であり、目視で滲みが見られた。 In contrast, Comparative Example 5 in which pretreatment was performed using a composition containing a cationic surfactant and no acid, and an acid and a surfactant other than the cationic surfactant and the amphoteric surfactant were included. In Comparative Examples 1 to 4 in which pretreatment was performed using the composition, the difference in line width from the design value exceeded 100 μm, and bleeding was observed visually. In all of the comparative examples, the difference between the wetting index of the copper substrate and the surface tension of the ink was +3 or more, and bleeding was observed visually.
Claims (5)
酸と、カチオン系界面活性剤および両性界面活性剤のうちの少なくともいずれか１種と、水と、を含む組成物からなることを特徴とする金属基材用表面処理剤。A metal substrate surface treatment agent that is used prior to forming a pattern coating film by applying ink by an inkjet method on a metal substrate,
A surface treatment agent for a metal substrate, comprising a composition containing an acid, at least one of a cationic surfactant and an amphoteric surfactant, and water.
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| JP2015068418 | 2015-03-30 | ||
| PCT/JP2015/073423 WO2016111036A1 (en) | 2015-01-07 | 2015-08-20 | Surface treatment agent for metal base |
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| JP6710402B2 (en) * | 2017-10-23 | 2020-06-17 | メック株式会社 | Method for producing film-forming substrate and surface treatment agent |
| CN112020234A (en) * | 2019-05-31 | 2020-12-01 | 广东高仕电研科技有限公司 | Preparation method of PCB and PCB |
| JP7516927B2 (en) | 2020-07-06 | 2024-07-17 | コニカミノルタ株式会社 | Inkjet recording liquid set and image forming method using said inkjet recording liquid set |
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| JPWO2016111035A1 (en) | 2017-11-02 |
| WO2016111036A1 (en) | 2016-07-14 |
| WO2016111035A1 (en) | 2016-07-14 |
| JP6779136B2 (en) | 2020-11-04 |
| JP6578304B2 (en) | 2019-09-18 |
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