CN102762627A - Two-liquid mixing first and second liquids and method for producing printed circuit board - Google Patents
Two-liquid mixing first and second liquids and method for producing printed circuit board Download PDFInfo
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- CN102762627A CN102762627A CN201280000309XA CN201280000309A CN102762627A CN 102762627 A CN102762627 A CN 102762627A CN 201280000309X A CN201280000309X A CN 201280000309XA CN 201280000309 A CN201280000309 A CN 201280000309A CN 102762627 A CN102762627 A CN 102762627A
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- liquid
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- organic solvent
- petroleum naphtha
- boiling point
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- 239000007788 liquid Substances 0.000 title claims abstract description 306
- 238000002156 mixing Methods 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 238000004821 distillation Methods 0.000 claims abstract description 157
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims description 109
- 239000003960 organic solvent Substances 0.000 claims description 107
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 97
- 239000003208 petroleum Substances 0.000 claims description 79
- 238000009835 boiling Methods 0.000 claims description 77
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 74
- KVXNKFYSHAUJIA-UHFFFAOYSA-N acetic acid;ethoxyethane Chemical compound CC(O)=O.CCOCC KVXNKFYSHAUJIA-UHFFFAOYSA-N 0.000 claims description 72
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 68
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 62
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 28
- 229910000679 solder Inorganic materials 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 150000004292 cyclic ethers Chemical group 0.000 abstract description 8
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 abstract 2
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- 239000000758 substrate Substances 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 239000000463 material Substances 0.000 description 8
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- 239000003963 antioxidant agent Substances 0.000 description 6
- 235000019439 ethyl acetate Nutrition 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
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- 238000011156 evaluation Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
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- 238000007650 screen-printing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
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- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- 239000000470 constituent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
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- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 238000010792 warming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/62—Arrangements for conducting electric current to or from the semiconductor body, e.g. lead-frames, wire-bonds or solder balls
-
- 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
- H05K3/285—Permanent coating compositions
- H05K3/287—Photosensitive compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Materials For Photolithography (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
Abstract
Provided are a first and second liquid that are two-liquid mixing type and that have superior miscibility of the first and second liquid. The two-liquid mixing first and second liquids are liquids for obtaining a photosensitive composition that is a mixture. The photosensitive composition contains at least two selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a naphtha having, in the distillation characteristics thereof, a first drop point of at least 150 DEG C and a last point of no greater than 290 DEG C. The first liquid contains a polymeric polymer. The second liquid contains a compound having a cyclic ether group. The first and second liquids contain at least one selected from the group consisting of dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, and a naphtha having, in the distillation characteristics thereof, a first drop point of at least 150 DEG C and a last point of no greater than 290 DEG C.
Description
Technical field
The present invention relates to first, second liquid of a kind of two liquid mixed types of the photosensitive composite that is used to obtain form of mixtures.More specifically, the present invention relates to a kind of being preferred for is forming soldering-resistance layer or is being equipped with the method for manufacture of the printed wiring board of first, second liquid of the two liquid mixed types that form catoptrical etchant resist on the substrate of light-emitting diode chip for backlight unit and first, second liquid that use has this two liquid mixed type on the substrate.
Background technology
Protect printed wiring board to avoid the protective membrane of high temperature scolding tin damage as being used to, soldering-resistance layer can be widely used.
In addition, in various electronics applications, on printed wiring board, be equipped with photodiode (below, abbreviate LED as) chip.The light that sends from LED,, on printed wiring board, be formed with white solder masks sometimes in order also to utilize the light of the upper face side that arrives above-mentioned printed wiring board.At this moment, not only can utilize the light that shines directly into from the surface of led chip with the printed wiring board opposition side, also can utilize the upper face side that arrives printed wiring board and by reflected light that white solder masks reflected.Therefore, can improve the utilising efficiency of the light that produces by LED.
Example as the material that is used to form above-mentioned white solder masks; In following patent documentation 1; Disclose a kind of erosion resistant, said erosion resistant contains the dealcoholization that utilizes epoxy resin and water-disintegrable organoalkoxysilane and the silane-modified epoxy resin that contains alkoxyl group that obtains and further comprise the polycarboxylic acid resin that contains unsaturated group, thinner, Photoepolymerizationinitiater initiater and solidify the adaptation imparting agent.
In following patent documentation 2, disclose a kind of white solder resist material that contains carboxy resin, Photoepolymerizationinitiater initiater, epoxy compounds, Titanium Dioxide (Rutile) Top grade and thinner that comprises with aromatic nucleus.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2007-249148 communique
Patent documentation 2: TOHKEMY 2007-322546 communique
Summary of the invention
The problem that invention will solve
In order on substrate, to form etchant resist,, can't be coated with erosion resistant equably sometimes and produce crawling in coating on the substrate as under the situation of the existing erosion resistant putting down in writing in the patent documentation 1 ~ 2.For example utilize silk screen printing that existing erosion resistant is coated under the situation on the substrate, in the erosion resistant layer that is coated with, finding the inequality of striated sometimes.
The object of the present invention is to provide the method for manufacture of the printed wiring board of first, second liquid of a kind of two liquid mixed types and first, second liquid that use has this two liquid mixed type; Wherein, The Combination of this first, second liquid is excellent and be photosensitive composite when being coated on the coating object parts being mixed with first, second mixtures of liquids, can suppress uneven and is coated with equably.
Be used to solve the means of problem
According to main aspect of the present invention; Provide it to be used to obtain first, second liquid as two liquid mixed types of the photosensitive composite of mixture; First, second liquid of this two liquid mixed type is for mixing this first, second liquid liquid before; Wherein, Being mixed with said first, second mixtures of liquids is that photosensitive composite integral body comprises: have polymerizable polymer, the Photoepolymerizationinitiater initiater of carboxyl, the compound with ring-type ether, titanium oxide and organic solvent; In the said photosensitive composite; As said organic solvent; To comprise the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics be more than 150 ℃ and distillation characteristics (proterties is stayed in steaming) in final boiling point be at least two kinds in the petroleum naphtha below 290 ℃; Said first liquid comprises said polymerizable polymer; And comprising the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least a part as said organic solvent in the petroleum naphtha below 290 ℃; Said second liquid comprises said compound with ring-type ether, and to comprise the over point that is selected from glycol ether monoethyl ether acetate, DPG monomethyl ether and the distillation characteristics be more than 150 ℃ and the final boiling point in the distillation characteristics is at least a part as said organic solvent in the petroleum naphtha below 220 ℃, and said first liquid comprises said Photoepolymerizationinitiater initiater or comprises said titanium oxide or comprise said Photoepolymerizationinitiater initiater and said titanium oxide; Do not comprise under the situation of said Photoepolymerizationinitiater initiater at said first liquid; Said second liquid comprises said Photoepolymerizationinitiater initiater, does not comprise under the situation of said titanium oxide at said first liquid, and said second liquid comprises said titanium oxide.
In the method for manufacture of printed wiring board of the present invention; Printed wiring board possesses the printed wiring board main body that has circuit on the surface, the lip-deep soldering-resistance layer that is provided with circuit that is stacked in this printed wiring board main body; This method comprises following operation: mix first, second liquid, the solder resist compsn that obtains being mixed with said first, second liquid is the operation of photosensitive composite; Have on the surface on the surface that is provided with circuit of printed wiring board main body of circuit; It is photosensitive composite that coating mixed has the solder resist compsn of said first, second liquid; Formation is stacked in the operation of the lip-deep soldering-resistance layer that is provided with said circuit of said printed wiring board main body; The solder resist compsn that is mixed with said first, second liquid is that photosensitive composite integral body comprises polymerizable polymer, the Photoepolymerizationinitiater initiater with carboxyl, the compound with ring-type ether, titanium oxide and organic solvent; It is more than 150 ℃ that said photosensitive composite comprises the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is that in the petroleum naphtha below 290 ℃ at least two kinds are as said organic solvent; Said first liquid comprises said polymerizable polymer; And comprising the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least a part as said organic solvent in the petroleum naphtha below 290 ℃; Said second liquid comprises said compound with ring-type ether; And to comprise the over point that is selected from glycol ether monoethyl ether acetate, DPG monomethyl ether and the distillation characteristics be more than 150 ℃ and the final boiling point in the distillation characteristics is at least a in the petroleum naphtha below 220 ℃; Said first liquid comprises said Photoepolymerizationinitiater initiater or comprises said titanium oxide or comprise said Photoepolymerizationinitiater initiater and said titanium oxide; Do not comprise under the situation of said Photoepolymerizationinitiater initiater at said first liquid; Said second liquid comprises said Photoepolymerizationinitiater initiater, does not comprise under the situation of said titanium oxide at said first liquid, and said second liquid comprises said titanium oxide.
In certain particular aspects of the method for manufacture of first, second liquid of two liquid mixed types of the present invention and printed wiring board of the present invention, it is more than 150 ℃ that said first liquid comprises the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is at least two kinds of parts as said organic solvent in the petroleum naphtha below 290 ℃.
In other particular aspects of the method for manufacture of first, second liquid of two liquid mixed types of the present invention and printed wiring board of the present invention, said first liquid comprises DPG monomethyl ether and glycol ether monoethyl ether acetate at least as the part of said organic solvent or to comprise over point in glycol ether monoethyl ether acetate and the distillation characteristics at least be more than 150 ℃ and the final boiling point in the distillation characteristics is that petroleum naphtha below 290 ℃ is as the part of said organic solvent.
In other particular aspects of the method for manufacture of first, second liquid of two liquid mixed types of the present invention and printed wiring board of the present invention, it is more than 150 ℃ that said first liquid comprises over point in DPG monomethyl ether and the distillation characteristics at least and the final boiling point in the distillation characteristics is that petroleum naphtha below 290 ℃ is as the part of said organic solvent.
In other particular aspects of the method for manufacture of first, second liquid of two liquid mixed types of the present invention and printed wiring board of the present invention; Said photosensitive composite contains the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics be more than 150 ℃ and the final boiling point in the distillation characteristics be in the petroleum naphtha below 220 ℃ at least two kinds as said organic solvent, the over point in the said distillation characteristics in said first liquid is more than 150 ℃ and the final boiling point in the distillation characteristics is that petroleum naphtha below 290 ℃ is that over point in the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 220 ℃.
In other particular aspects of the method for manufacture of first, second liquid of two liquid mixed types of the present invention and printed wiring board of the present invention, said first liquid comprises said Photoepolymerizationinitiater initiater.
In other particular aspects of the method for manufacture of first, second liquid of two liquid mixed types of the present invention and printed wiring board of the present invention, said first liquid comprises said titanium oxide.
In another other the particular aspects of the method for manufacture of first, second liquid of two liquid mixed types of the present invention and printed wiring board of the present invention, said first liquid comprises said photopolymerization and begins agent and said titanium oxide.
In first, second liquid of two liquid mixed types of the present invention, the photosensitive composite that is mixed with said first, second liquid can be preferably used as the solder resist compsn.
In first, second liquid of two liquid mixed types of the present invention, the photosensitive composite that preferably is mixed with said first, second liquid is the solder resist compsn.
The invention effect
First, second liquid of the two liquid mixed types that the present invention relates to; It is used to obtain the photosensitive composite as mixture; First, second liquid of this two liquid mixed type is for mixing this first, second liquid liquid before; Wherein, Being mixed with said first, second mixtures of liquids is that photosensitive composite integral body comprises: have polymerizable polymer, the Photoepolymerizationinitiater initiater of carboxyl, the compound with ring-type ether, titanium oxide and organic solvent; In the said photosensitive composite; As said organic solvent; Comprising the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least two kinds in the petroleum naphtha below 290 ℃; Said first liquid comprises said polymerizable polymer, and to comprise the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics be more than 150 ℃ and the final boiling point in the distillation characteristics is at least a part as said organic solvent in the petroleum naphtha below 290 ℃, and said second liquid comprises said compound with ring-type ether; And comprising the over point that is selected from glycol ether monoethyl ether acetate, DPG monomethyl ether and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least a part as said organic solvent in the petroleum naphtha below 220 ℃; Said first liquid comprises said Photoepolymerizationinitiater initiater or comprises said titanium oxide or comprise said Photoepolymerizationinitiater initiater and said titanium oxide, and therefore, the Combination of said first, second liquid is excellent; In the time of on mixed photosensitive composite being coated on coating object parts, can suppressing uneven and be coated with equably.
Description of drawings
Fig. 1 is that front cross-sectional view is blocked in the part, schematically shows an example of the LED equipment with etchant resist that use obtains by first, second liquid of the two liquid mixed types of an embodiment of the invention.
Description of symbols
1...LED equipment
2... substrate
2a... upper surface
3... etchant resist
3a... upper surface
4a, 4b... electrode
7...LED chip
7a... lower surface
8a, 8b... terminal
9a, 9b... scolding tin
Embodiment
Below, the present invention is elaborated.
First, second liquid of the two liquid mixed types that the present invention relates to is used to obtain the photosensitive composite of form of mixtures.First, second liquid of the two liquid mixed types that the present invention relates to is the combination (kit) that is used to obtain the photosensitive composite of form of mixtures.First, second liquid of two liquid mixed types of the present invention uses after mixing.First, second liquid of two liquid mixed types of the present invention is for mixing this first, second liquid liquid before.First, second liquid before mixing is the photosensitive composite before mixing.First, second mixtures of liquids that is mixed with two liquid mixed types of the present invention is that photosensitive composite integral body comprises polymerizable polymer (A), the Photoepolymerizationinitiater initiater (B) with carboxyl, the compound (C) with ring-type ether, titanium oxide (D) and organic solvent (E) (below, sometimes organic solvent contained in the photosensitive composite integral body is designated as organic solvent (E)).Being mixed with above-mentioned first, second mixtures of liquids is photosensitive composite, and this photosensitive composite integral body of institute's blended comprises polymerizable polymer (A), the Photoepolymerizationinitiater initiater (B) with carboxyl, the compound (C) with ring-type ether, titanium oxide (D) and organic solvent (E).
It is more than 150 ℃ that above-mentioned photosensitive composite contains the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is that in the petroleum naphtha below 290 ℃ at least two kinds are as organic solvent (E).
Above-mentioned first liquid contains above-mentioned polymerizable polymer (A); And contain and be selected from the DPG monomethyl ether, the over point in glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least a part as said organic solvent (E) in the petroleum naphtha below 290 ℃.Above-mentioned second liquid contains above-mentioned compound (C) with ring-type ether, and to comprise the over point that is selected from glycol ether monoethyl ether acetate, DPG monomethyl ether and the distillation characteristics be more than 150 ℃ and the final boiling point in the distillation characteristics is at least a part as above-mentioned organic solvent (E) in the petroleum naphtha below 220 ℃.
Above-mentioned first liquid contain above-mentioned Photoepolymerizationinitiater initiater (B) contain above-mentioned titanium oxide (D) or contain above-mentioned Photoepolymerizationinitiater initiater (B) and above-mentioned titanium oxide (D) both.Do not comprise under the situation of above-mentioned Photoepolymerizationinitiater initiater (B) at above-mentioned first liquid, above-mentioned second liquid comprises above-mentioned Photoepolymerizationinitiater initiater (B).Do not comprise under the situation of above-mentioned titanium oxide (D) at above-mentioned first liquid, above-mentioned second liquid comprises above-mentioned titanium oxide (D).
Above-mentioned Photoepolymerizationinitiater initiater (B) and above-mentioned titanium oxide (D) can be included in respectively in first liquid, also can be included in second liquid, also can be included in first liquid and second liquid.
In addition; The polymerizable monomer of after first, second liquid of two liquid mixed types of the present invention comprises, stating or comprise after under the situation of the inhibitor stated; Polymerizable monomer and inhibitor can be included in first liquid respectively; Can be included in second liquid, also can be included in first liquid and second liquid.
Through the above-mentioned formation in first, second liquid that adopts two liquid mixed types of the present invention, can improve the Combination of above-mentioned first, second liquid.And then, during photosensitive composite on coating such as substrate object parts after the coating mixed, can suppress the inequality that produces mainly due to titanium oxide and be coated with equably.Particularly, during photosensitive composite after utilizing silk screen printing to come coating mixed, can suppress the inequality of striated.First, second liquid of preferred two liquid mixed types of the present invention is first, second liquid that utilizes the two liquid mixed types that silk screen printing is coated with.
Preferred above-mentioned Photoepolymerizationinitiater initiater (B) is included in first liquid rather than is included in second liquid.At this moment, the Combination of above-mentioned first, second liquid further uprises, and can further be coated with photosensitive composite equably.
Preferred above-mentioned titanium oxide (D) is included in first liquid rather than is included in second liquid.At this moment, the dispersiveness of titanium oxide (D) uprises, and then the Combination of above-mentioned first, second liquid further uprises, and can further be coated with photosensitive composite equably.
Both are included in preferred above-mentioned Photoepolymerizationinitiater initiater (B) and above-mentioned titanium oxide (D) in first liquid rather than are included in second liquid.At this moment, the dispersiveness of titanium oxide (D) further uprises, and then the Combination of above-mentioned first, second liquid further uprises, and can be coated with photosensitive composite more equably.
Below, each contained composition in first, second liquid of two liquid mixed types of the present invention and the mixed photosensitive composite is elaborated.
(polymerizable polymer (A))
Above-mentioned polymerizable polymer (A) has carboxyl.Polymerizable polymer (A) with carboxyl has polymerizability, can carry out polymerization.Because above-mentioned polymerizable polymer (A) has carboxyl, it is good that the development property of photosensitive composite becomes.As above-mentioned polymerizable polymer (A), for example can enumerate: have carboxyl vinyl resin, have the epoxy resin of carboxyl and have the olefin resin of carboxyl.Need to prove that " resin " is not limited to hard resin, also comprise aqueous resin and oligopolymer.
Above-mentioned polymerizable polymer (A) is preferably the following resin (a) ~ (e) that contains carboxyl.
(a) resin that contains carboxyl that obtains through unsaturated carboxylic acid and copolymerization with compound of polymerizability unsaturated double-bond
(b) resin that contains carboxyl that obtains of (methyl) acrylic copolymeric resin (b1) through containing carboxyl and the reaction that in a molecule, has the compound (b2) of oxyethane ring and ethene property polymerizability unsaturated double-bond
(c) unsaturated monocarboxylic and following multipolymer are reacted after; The secondary hydroxyl that makes the reactant of saturated or unsaturated multi-anhydride and generation reacts and the resin that contains carboxyl that obtains, and said multipolymer is the compound and the polymkeric substance with compound formation of polymerizability unsaturated double-bond that in a molecule, has an epoxy group(ing) and polymerizability unsaturated double-bond respectively
(d) saturated or unsaturated multi-anhydride and the polymkeric substance that contains hydroxyl are reacted after, the polymkeric substance with carboxyl that makes the compound that in a molecule, has an epoxy group(ing) and polymerizability unsaturated double-bond respectively and generation reacts and the resin that contains hydroxyl and carboxyl that obtains
(e) epoxy compounds with aromatic nucleus and saturated polybasic acid acid anhydride or unsaturated multi-anhydride are reacted and the resin that obtains or make epoxy compounds and after the compound that has a unsaturated double-bond at least and contain carboxyl reacts, further make it to react and the resin that obtains with saturated polybasic acid acid anhydride or unsaturated multi-anhydride with aromatic nucleus.
In above-mentioned photosensitive composite 100 weight %, above-mentioned content with polymerizable polymer (A) of carboxyl is preferably more than the 3 weight %, more preferably more than the 5 weight %, is preferably below the 50 weight %, more preferably below the 40 weight %.
The content of above-mentioned polymerizable polymer (A) with carboxyl is more than above-mentioned lower limit and above-mentioned upper limit when following, and it is good that the solidified nature of photosensitive composite becomes.
(Photoepolymerizationinitiater initiater (B))
Above-mentioned photosensitive composite contains Photoepolymerizationinitiater initiater (B), therefore, photosensitive composite is solidified.Photoepolymerizationinitiater initiater (B) is not special to be limited.Photoepolymerizationinitiater initiater (B) can only use a kind of, also can make up use two or more.
As above-mentioned Photoepolymerizationinitiater initiater (B), for example can enumerate: acylphosphine oxide, halomethylation triazine, halogen Jia Jiization oxadiazole, imidazoles, bitter almond oil camphor, benzoin alkylether, anthraquinone, benzanthrone, UVNUL MS-40, methyl phenyl ketone, thioxanthone, benzoic ether, acridine, azophenlyene, luxuriant titanium, alpha-aminoalkyl benzophenone, oxime and these verivate.Above-mentioned Photoepolymerizationinitiater initiater (B) can only use a kind of, also can two or more combinations use.
With respect to above-mentioned polymerizable polymer (A) 100 weight parts with carboxyl, the content of above-mentioned Photoepolymerizationinitiater initiater (B) is preferably more than 0.1 weight part, more preferably more than 1 weight part, is preferably below 30 weight parts, more preferably below 15 weight parts.The content of above-mentioned Photoepolymerizationinitiater initiater (B) can further improve the photosensitivity of photosensitive composite more than above-mentioned lower limit and above-mentioned upper limit when following.
(compound (C)) with ring-type ether
From the purpose that cuts out processibility etc. that improves etchant resist, above-mentioned photosensitive composite comprises the compound (C) with cyclic ether skeleton.In addition, through using above-mentioned compound (C) with cyclic ether skeleton, it is good that the solidified nature of photosensitive composite also becomes.
As above-mentioned compound (C), for example can enumerate: phenolic resin varnish type epoxy resin, chelating type epoxy resin, the oxalic dialdehyde type epoxy resin of hetero ring type epoxy resin such as bisphenol-s epoxy resin, o-phthalic acid diglycidyl ester resin, cyamelide three-glycidyl ester, bis-xylene phenol-type epoxy resin, bisphenol-type epoxy resin, Fourth Ring oxygen propoxy-xylenol ethane resin, bisphenol A type epoxy resin, bisphenol-A epoxy resin, Bisphenol F type resin, brominated bisphenol a type epoxy resin, phenolic resin varnish type epoxy resin, cresols phenolic resin varnish type epoxy resin, alicyclic epoxy resin, dihydroxyphenyl propane, contain amino epoxy resin, rubber modified epoxy resin, Dicyclopentadiene (DCPD) phenol aldehyde type epoxy resin, modifying epoxy resin by organosilicon and 6-caprolactone modified epoxy with cyclic ether skeleton.Above-mentioned compound (C) with cyclic ether skeleton can only use a kind of, also can two or more combinations use.
Above-mentioned compound (C) with cyclic ether skeleton reacts with the carboxyl that above-mentioned polymerizable polymer (A) with carboxyl is had, and plays a role so that photosensitive composite solidifies.
With respect to above-mentioned polymerizable polymer (A) 100 weight parts with carboxyl; Above-mentioned content with compound (C) of cyclic ether skeleton is preferably more than 0.1 weight part; More preferably more than 1 weight part, be preferably below 50 weight parts, more preferably below 30 weight parts.Above-mentioned content with compound (C) of cyclic ether skeleton is the above and above-mentioned upper limit of above-mentioned lower limit when following, can further improve the electrical insulating property of etchant resist.
(titanium oxide (D))
Above-mentioned photosensitive composite comprises titanium oxide (D), therefore, can form the high cured article films such as etchant resist of reflectivity.Titanium oxide (D) contained in the above-mentioned photosensitive composite does not limit especially.Titanium oxide (D) can only use a kind of, also can two or more combinations use.
Compare with the situation of other mineral filler outside using titanium oxide (D), can form the high etchant resist of reflectivity through using above-mentioned titanium oxide (D).
Above-mentioned titanium oxide (D) is preferably Titanium Dioxide (Rutile) Top grade or anatase-type titanium oxide.Through using Titanium Dioxide (Rutile) Top grade, can form the further excellent etchant resist of heat-resisting xanthochromia property.Above-mentioned anatase-type titanium oxide is also lower than the hardness of Titanium Dioxide (Rutile) Top grade.Therefore, through using anatase-type titanium oxide, can improve the processibility of etchant resist.
Above-mentioned titanium oxide (D) preferably comprises through Si oxide or silicoorganic compound and has carried out the surface-treated Titanium Dioxide (Rutile) Top grade.In above-mentioned titanium oxide (D) 100 weight %, the content that carries out the Titanium Dioxide (Rutile) Top grade after the surface treatment through above-mentioned Si oxide or silicoorganic compound is preferably more than the 10 weight %, and more preferably 30 weight % are above and below the 100 weight %.The total content of above-mentioned titanium oxide (D) can be for having carried out the surface-treated Titanium Dioxide (Rutile) Top grade through above-mentioned Si oxide or silicoorganic compound.Carry out the surface-treated Titanium Dioxide (Rutile) Top grade through using through above-mentioned Si oxide or silicoorganic compound, can further improve the heat-resisting xanthochromia property of etchant resist.
As the Titanium Dioxide (Rutile) Top grade that carries out through Si oxide or silicoorganic compound after the surface treatment, for example can enumerate: rutile chlorine method titanium oxide is that the goods number of the former industry corporate system of stone: CR-90 or rutile sulfuric acid process titanium oxide are the goods number of the former industry corporate system of stone: R-550 etc.
In above-mentioned photosensitive composite 100 weight %, the content of titanium oxide (D) is preferably more than the 3 weight %, more preferably more than the 10 weight %; Further be preferably more than the 15 weight %; Be preferably below the 80 weight %, more preferably below the 75 weight %, further be preferably below the 70 weight %.If the content of titanium oxide (D) is more than the above-mentioned lower limit and below the above-mentioned upper limit, when then etchant resist is exposed at high temperature, be difficult for xanthochromia.And then, can easily prepare photosensitive composite with the viscosity that is suitable for being coated with.
(organic solvent (E))
Above-mentioned photosensitive composite comprises organic solvent (E).The photosensitive composite that is mixed with above-mentioned first, second liquid comprises organic solvent (E).Above-mentioned photosensitive composite comprises at least two kinds of organic solvents.Contained organic solvent (E1) in preferred above-mentioned first liquid (below; Sometimes organic solvent contained in first liquid is designated as organic solvent (E1)) and above-mentioned second liquid in contained organic solvent (E2) (below, sometimes organic solvent contained in second liquid is designated as organic solvent (E2)) difference.
As common known organic solvent, can enumerate: petroleum-type solvent such as aliphatic hydrocarbon such as ester class, octane, decane such as glycol ethers such as ketones such as methyl ethyl ketone, pimelinketone, toluene, YLENE, tetramethyl-benzene etc. are aromatic hydrocarbon based, cellosolve, methylcyclohexane, ethylene glycol butyl ether, Trivalin SF, methyl carbitol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, DPG monomethyl ether, DPG diethyl ether, tripropylene glycol monomethyl ether, vinyl acetic monomer, N-BUTYL ACETATE, n-Butyl lactate, cellosolve acetic ester, butyl cellosolve acetate, Trivalin SF acetic ester, acetate of butyl carbitol, propylene glycol methyl ether acetate, glycol ether monoethyl ether acetate, DPG methyl ether acetate, Texacar PC and sherwood oil, petroleum naphtha etc.
In above-mentioned organic solvent, it is more than 150 ℃ that above-mentioned first liquid must comprise the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is at least a part as above-mentioned organic solvent (E) in the petroleum naphtha below 290 ℃.Over point in DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least a for organic solvent (E1) in the petroleum naphtha below 290 ℃.
In addition; In above-mentioned organic solvent, it is more than 150 ℃ that above-mentioned second liquid comprises the over point that is selected from glycol ether monoethyl ether acetate, DPG monomethyl ether and the distillation characteristics and the final boiling point in the distillation characteristics is at least a part as above-mentioned organic solvent (E) in the petroleum naphtha below 220 ℃.To be selected from over point in glycol ether monoethyl ether acetate, DPG monomethyl ether and the distillation characteristics be more than 150 ℃ and the final boiling point in the distillation characteristics is that at least a in the petroleum naphtha below 220 ℃ is organic solvent (E2).
Through in first, second liquid, containing such organic solvent (E1), (E2) respectively, the Combination of above-mentioned first, second liquid significantly improves.Inequality after using specific above-mentioned organic solvent (E1), (E2) and then in first liquid and second liquid, containing the coating that specific above-mentioned organic solvent (E1), (E2) go far towards to improve the Combination of above-mentioned first, second liquid and suppress mixed photosensitive composite respectively separately.
The value that above-mentioned " over point in the distillation characteristics " and above-mentioned " final boiling point in the distillation characteristics " expression is measured according to JlSK2254 " petroleum product-distillation test method ".
It is more than 150 ℃ that above-mentioned first liquid also preferably comprises over point in DPG monomethyl ether and the distillation characteristics and the final boiling point in the distillation characteristics is at least a part as above-mentioned organic solvent (E) in the petroleum naphtha below 220 ℃.It is more than 150 ℃ that above-mentioned first liquid comprises over point in DPG monomethyl ether and the distillation characteristics and the final boiling point in the distillation characteristics is under both situation as the part of above-mentioned organic solvent (E) of petroleum naphtha below 220 ℃; This moment, above-mentioned first liquid can comprise, and also can not comprise titanium oxide.
In above-mentioned first liquid; Part as above-mentioned organic solvent (E); Can comprise the DPG monomethyl ether; Also can comprise the glycol ether monoethyl ether acetate, can comprise over point in the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 290 ℃, and also can comprise over point in the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 220 ℃.
In addition; In above-mentioned second liquid; Part as above-mentioned organic solvent (E); Can comprise the glycol ether monoethyl ether acetate, also can comprise the DPG monomethyl ether, can also comprise over point in the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 220 ℃.
It is more than 150 ℃ that above-mentioned photosensitive composite comprises the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is at least two kinds in the petroleum naphtha below 290 ℃.
It is more than 150 ℃ that above-mentioned photosensitive composite also can comprise over point in DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is these the three kinds of materials of petroleum naphtha below 290 ℃.
Consider that from the viewpoint that further is coated with photosensitive composite equably above-mentioned photosensitive composite preferably comprises DPG monomethyl ether and glycol ether monoethyl ether acetate at least or comprises over point in glycol ether monoethyl ether acetate and the distillation characteristics at least is more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 290 ℃.
Consider that from the viewpoint that further is coated with photosensitive composite equably above-mentioned photosensitive composite preferably comprises DPG monomethyl ether and glycol ether monoethyl ether acetate at least.At this moment, also can to comprise the over point in the distillation characteristics be more than 150 ℃ to above-mentioned photosensitive composite and the final boiling point in the distillation characteristics is the petroleum naphtha below 290 ℃.
Consider that from the viewpoint that further is coated with photosensitive composite equably it is more than 150 ℃ that above-mentioned photosensitive composite preferably comprises over point in glycol ether monoethyl ether acetate and the distillation characteristics at least and the final boiling point in the distillation characteristics is the petroleum naphtha below 290 ℃.At this moment, above-mentioned first liquid preferably comprises the DPG monomethyl ether.
Consider that from the viewpoint that further is coated with photosensitive composite equably it is more than 150 ℃ that above-mentioned photosensitive composite preferably comprises over point in DPG monomethyl ether and the distillation characteristics at least and the final boiling point in the distillation characteristics is the petroleum naphtha below 290 ℃.At this moment, above-mentioned first liquid can comprise the glycol ether monoethyl ether acetate.
Consider that from the viewpoint that further is coated with photosensitive composite equably the over point in the distillation characteristics in the above-mentioned photosensitive composite is more than 150 ℃ and the final boiling point in the distillation characteristics is that to be preferably over point in the distillation characteristics be more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 220 ℃ for petroleum naphtha below 290 ℃.
In above-mentioned first liquid; As the part of above-mentioned organic solvent (E), preferably comprising the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least two kinds in the petroleum naphtha below 290 ℃.At this moment, the Combination of above-mentioned first, second liquid can be further improved, and photosensitive composite can be further be coated with equably.
In above-mentioned first liquid; As the part of above-mentioned organic solvent (E), can comprise over point in DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is these the three kinds of materials of petroleum naphtha below 290 ℃.
In above-mentioned first liquid; As the part of above-mentioned organic solvent (E), preferably comprising DPG monomethyl ether and glycol ether monoethyl ether acetate at least or comprising over point in glycol ether monoethyl ether acetate and the distillation characteristics at least is more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 290 ℃.At this moment, the Combination of above-mentioned first, second liquid can be further improved, and photosensitive composite can be further be coated with equably.
From further improving the Combination of above-mentioned first, second liquid; And the viewpoint that further is coated with photosensitive composite is equably considered; In above-mentioned first liquid; As the part of above-mentioned organic solvent (E), preferably comprise DPG monomethyl ether and glycol ether monoethyl ether acetate at least.At this moment, can to comprise the over point in the distillation characteristics be more than 150 ℃ to above-mentioned first liquid and the final boiling point in the distillation characteristics is the petroleum naphtha below 290 ℃.
From further improving the Combination of above-mentioned first, second liquid; And the viewpoint that further is coated with photosensitive composite is equably considered; In above-mentioned first liquid; As the part of above-mentioned organic solvent (E), the preferred over point that comprises at least in glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 290 ℃.At this moment, above-mentioned first liquid preferably comprises the DPG monomethyl ether.
From further improving the Combination of above-mentioned first, second liquid; And the viewpoint that further is coated with photosensitive composite is equably considered; In above-mentioned first liquid; As the part of above-mentioned organic solvent (E), the preferred over point that comprises at least in DPG monomethyl ether and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 290 ℃.At this moment, above-mentioned first liquid can comprise the glycol ether monoethyl ether acetate.
From further improving the Combination of above-mentioned first, second liquid; And the viewpoint that further is coated with photosensitive composite is equably considered; In the above-mentioned photosensitive composite; As above-mentioned organic solvent; Preferably comprise and be selected from the DPG monomethyl ether; Over point in glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least two kinds in the petroleum naphtha below 220 ℃, and the over point in the distillation characteristics in above-mentioned first liquid is more than 150 ℃ and the final boiling point in the distillation characteristics is that to be preferably over point in the distillation characteristics be more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 220 ℃ for petroleum naphtha below 290 ℃.
Above-mentioned first liquid can not comprise the glycol ether monoethyl ether acetate.
In above-mentioned second liquid; As the part of above-mentioned organic solvent (E), can comprise the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least two kinds in the petroleum naphtha below 220 ℃.
In above-mentioned second liquid; As the part of above-mentioned organic solvent (E), can comprise over point in glycol ether monoethyl ether acetate, DPG monomethyl ether and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is these the three kinds of materials of petroleum naphtha below 220 ℃.
From further improving the Combination of above-mentioned first, second liquid; And the viewpoint that further is coated with photosensitive composite is equably considered; In above-mentioned second liquid; As the part of above-mentioned organic solvent (E), preferably comprise glycol ether monoethyl ether acetate and DPG monomethyl ether at least.At this moment, also can to comprise the over point in the distillation characteristics be more than 150 ℃ to above-mentioned second liquid and the final boiling point in the distillation characteristics is the petroleum naphtha below 220 ℃.
From further improving the Combination of above-mentioned first, second liquid; And the viewpoint that further is coated with photosensitive composite is equably considered; In above-mentioned second liquid; As the part of above-mentioned organic solvent (E), the preferred over point that comprises at least in glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 220 ℃.At this moment, above-mentioned second liquid preferably comprises the DPG monomethyl ether.
From further improving the Combination of above-mentioned first, second liquid; And the viewpoint that further is coated with photosensitive composite is equably considered; As far as above-mentioned second liquid; As the part of above-mentioned organic solvent (E), the preferred over point that comprises at least in DPG monomethyl ether and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is the petroleum naphtha below 220 ℃.At this moment, above-mentioned second liquid can comprise the glycol ether monoethyl ether acetate.
Above-mentioned second liquid also can not comprise the glycol ether monoethyl ether acetate.
The content of organic solvent (E) is not special to be limited.Consider the coating of photosensitive composite, organic solvent (E) can use with suitable content.In mixed photosensitive composite 100 weight %; The total content of above-mentioned organic solvent (E) (the total content of above-mentioned organic solvent (E1) and above-mentioned organic solvent (E2)) is preferably more than the 10 weight %; More preferably more than the 15 weight %, be preferably below the 60 weight %, more preferably below the 50 weight %.
The viewpoint that from the Combination that further improves above-mentioned first, second liquid, further is coated with photosensitive composite is equably considered; In first, second liquid integral body of two liquid mixed types; In preferred above-mentioned first liquid in the content of contained organic solvent (E1) and above-mentioned second liquid content of contained organic solvent (E2) count 1:99 ~ 99:1 with weight ratio; More preferably 1:9 ~ 9:1 further is preferably 2:8 ~ 8:2, is preferably 3:7 ~ 7:3 especially.In other words; In mixed photosensitive composite; In this photosensitive composite among the total content 100 weight % of contained above-mentioned organic solvent (E), in preferred above-mentioned first liquid in the content of contained organic solvent (El) and above-mentioned second liquid content of contained above-mentioned organic solvent (E2) count 1:99 ~ 99:1 with weight ratio, 1:9 ~ 9:1 more preferably; Further be preferably 2:8 ~ 8:2, be preferably 3:7 ~ 7:3 especially.
In the whole 100 weight % of first, second liquid of two liquid mixed types and in mixed photosensitive composite 100 weight %, the content of glycol ether monoethyl ether acetate can be for more than the 30 weight %.In above-mentioned first liquid, 100 weight %, the content of glycol ether monoethyl ether acetate can be for below the 50 weight %, also can be for more than the 55 weight %.
Comprise under the situation of two kinds of organic solvents at above-mentioned first liquid and above-mentioned second liquid comprises under the situation of two kinds of organic solvents; In above-mentioned first liquid and above-mentioned second liquid; The content of the organic solvent that preferred content is many and the content of poor organic solvent are counted 1:99 ~ 99:1 with weight ratio; More preferably 1:9 ~ 9:1 further is preferably 2:8 ~ 8:2, is preferably 3:7 ~ 7:3 especially.
Comprise under the situation of three kinds of organic solvents at above-mentioned first liquid and above-mentioned second liquid comprises under the situation of three kinds of organic solvents; In above-mentioned first liquid and above-mentioned second liquid; The content of the organic solvent of the content of the organic solvent that preferred content is maximum and content more than second is counted 1:99 ~ 99:1 with weight ratio; More preferably 1:9 ~ 9:1 further is preferably 2:8 ~ 8:2, is preferably 3:7 ~ 7:3 especially.At this moment, the lower limit of the content of the minimum organic solvent of content is not special limits.
(other composition)
In order further to improve solidified nature, above-mentioned photosensitive composite preferably comprises polymerizable monomer conduct and the different composition of the polymerizable polymer with carboxyl (A).Above-mentioned photosensitive composite preferably comprises polymerizable polymer (A) and the polymerizable monomer with carboxyl.Above-mentioned polymerizable monomer has polymerizability, can carry out polymerization.Above-mentioned polymerizable monomer is not special to be limited.Above-mentioned polymerizable monomer can only use a kind of, also can two or more combinations use.
Above-mentioned polymerizable monomer is preferably the monomer that contains the polymerizability unsaturated group.As the polymerizability unsaturated group in the above-mentioned polymerizable monomer, for example can enumerate: (methyl) acryl and vinyl ether group etc. have the functional group of polymerizability unsaturated double-bond.Wherein, because (methyl) acryl can improve the cross-linking density of etchant resist, so preferred.
The above-mentioned monomer that contains the polymerizability unsaturated group is preferably the compound with (methyl) acryl.As above-mentioned compound, can enumerate: the ethylene oxide adduct of polynary (methyl) the acrylate modified thing of the ethylene oxide adduct of the acrylate modified thing of two (methyl) of glycol such as terepthaloyl moietie, methoxyl group TEG, polyoxyethylene glycol or Ucar 35 or polyvalent alcohol, polyvalent alcohol or the propylene oxide adduct of polyvalent alcohol or phenol, phenol or (methyl) the acrylate modified thing of the propylene oxide adduct of phenol or (methyl) the acrylate modified thing or trimeric cyanamide (methyl) propenoate of glycidyl ethers such as glycerin diglycidyl ether or trihydroxymethylpropanyltri diglycidyl ether with (methyl) acryl.
As above-mentioned polyvalent alcohol, for example can enumerate: pinakon, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol and trihydroxyethyl isocyanuric acid ester.As (methyl) propenoate of above-mentioned phenol, for example can enumerate: the acrylate modified thing of two (methyl) of phenoxy (methyl) propenoate and dihydroxyphenyl propane.
" (methyl) acryl " is meant acryl and methacryloyl." (methyl) vinylformic acid " is meant vinylformic acid and methylacrylic acid." (methyl) propenoate " is meant propenoate and methacrylic ester.
Comprising under the situation of above-mentioned polymerizable monomer, having among the total 100 weight % of polymerizable polymer (A) of carboxyl at this polymerizable monomer and above-mentioned, it is above and below the 50 weight % that the content of above-mentioned polymerizable monomer is preferably 5 weight %.
The content of above-mentioned polymerizable monomer is the above and above-mentioned upper limit of above-mentioned lower limit when following, and photosensitive composite is fully solidified.And then the cross-linking density of etchant resist becomes suitably, can obtain sufficient resolving power, and etchant resist is difficult for xanthochromia.
The xanthochromic risk of soldering-resistance layer when exposing at high temperature in order to reduce, above-mentioned photosensitive composite preferably contains inhibitor.Above-mentioned inhibitor preferably has the lewis base property position.Consider that from further suppressing the xanthochromic viewpoint of etchant resist above-mentioned inhibitor is preferably and is selected from least a in phenol antioxidant, Phosphorus inhibitor and the amine antioxidants.Consider that from further suppressing the xanthochromic viewpoint of etchant resist above-mentioned inhibitor is preferably phenol antioxidant.That is, above-mentioned photosensitive composite preferably comprises phenol antioxidant.
Commercially available article as above-mentioned phenol antioxidant; Can enumerate: IRGANOX 1010, IRGANOX1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259 and IRGANOX 295 (more than; Be Ciba Japan corporate system), ADEKASTAB AO-30, ADEKASTAB AO-40, ADEKASTAB AO-50, ADEKASTAB AO-60, ADEKASTAB AO-70, ADEKASTAB AO-80, ADEKASTAB AO-90 and ADEKASTAB AO-330 (more than; Be the ADEKA corporate system), Sumilizer GA-80, SumilizerMDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F) and Sumilizer GP (more than; Be Sumitomo Chemical Co. Ltd.'s system), HOSTANOX O10, HOSTANOX O16, HOSTANOX O14 and HOSTANOX O3 (more than; Be the Clariant corporate system), Antage BHT, Antage W-300, Antage W-400 and Antage W500 (more than; Be chemical industrial company of Kawaguchi system) and SEENOX 224M and SEENOX 326M (more than, be shipro and change into corporate system) etc.
As above-mentioned Phosphorus inhibitor, can enumerate: cyclohexyl phosphine and triphenylphosphine etc.Commercially available article as above-mentioned Phosphorus inhibitor; Can enumerate: ADEKASTAB PEP-4C, ADEKASTABPEP-8, ADEKASTAB PEP-24G, ADEKASTAB PEP-36, ADEKASTABHP--10, ADEKASTAB 2112, ADEKASTAB 260, ADEKASTAB 522A, ADEKASTAB 1178, ADEKASTAB 1500, ADEKASTAB C, ADEKASTAB135A, ADEKASTAB 3010 and ADEKASTAB TPP (more than; Be the ADEKA corporate system), Sandostab P-EPQ and Hostanox PAR24 (more than; Be the Clariant corporate system) and JP-312L, JP-318-0, JPM-308, JPM-313, JPP-613M, JPP-31, JPP-2000PT and JPH-3800 (more than, be north of the city chemical industrial company system) etc.
As above-mentioned amine antioxidants; Can enumerate: triethylamine, Dyhard RU 100, trimeric cyanamide, ethyl diamino--S-triazine, 2; 4-diamino--S-triazine, 2,4-diamino--6-tolyl-S-triazine, 2,4-diamino--6-xylyl-S-triazine and quaternary ammonium salt derivative etc.
With respect to above-mentioned polymerizable polymer (A) 100 weight parts with carboxyl, the content of above-mentioned inhibitor is preferably more than 0.1 weight part, more preferably more than 5 weight parts, is preferably below 30 weight parts, more preferably below 15 weight parts.The content of above-mentioned inhibitor is the above and upper limit of above-mentioned lower limit when following, can form the further etchant resist of excellence of heat-resisting xanthochromia property.
In addition, above-mentioned photosensitive composite also can comprise tinting material, weighting agent, skimmer, solidifying agent, curing catalyst, releasing agent, surface treatment agent, fire retardant, viscosity modifier, dispersion agent, dispersing auxiliary, surface-modifying agent, softening agent, antiseptic-germicide, mould inhibitor, flow agent, stablizer, coupling agent, anti-sagging agent or fluor etc.
Above-mentioned photosensitive composite for example can prepare through mixing equably with three-roller through after mixing each gradation composition.
Make above-mentioned photosensitive composite solidified light source as being used to, can enumerate: the irradiating unit that sends ultraviolet ray or visible rays isoreactivity energy line.As above-mentioned light source, for example can enumerate: extra-high-pressure mercury vapour lamp, Deep UV lamp, high pressure mercury vapour lamp, Cooper-Hewitt lamp, metal-halide lamp and excimer laser.
These light sources can be selected according to the wavelength photoreceptor of the constituent of photosensitive composite is suitable.The irradiation energy of light can suit to select according to the thickness of expectation or the constituent of photosensitive composite.The irradiation energy of light is usually at 10 ~ 3000mJ/cm
2Scope in.
(LED equipment)
First, second liquid of two liquid mixed types of the present invention is preferred for forming the etchant resist of LED equipment, more preferably is used to form soldering-resistance layer.First, second liquid of two liquid mixed types of the present invention is preferably corrosion-resistant composition, is preferably the solder resist compsn.
The method of manufacture of printed wiring board of the present invention is used to make following printed wiring board, and it possesses the lip-deep etchant resist that is provided with foregoing circuit that the surface has the printed wiring board main body of circuit and is stacked in this printed wiring board main body.This etchant resist is formed by first, second liquid of two liquid mixed types of the present invention.
In Fig. 1, block the example that front cross-sectional view schematically shows the LED equipment with the formed soldering-resistance layer of first, second liquid that uses the two liquid mixed types that an embodiment of the present invention relates to local.
In LED equipment 1 shown in Figure 1, have by the formed etchant resist 3 of first, second liquid of two liquid mixed types at the upper surface 2a of substrate 2 lamination.Etchant resist 3 is a pattern film.Therefore, in a part of zone of the upper surface 2a of substrate 2, be not formed with etchant resist 3.The upper surface 2a that does not form etchant resist 3 parts at substrate 2 is provided with electrode 4a, 4b.Substrate 2 is preferably the printed wiring board main body.
At the upper surface 3a of etchant resist 3 lamination led chip 7 is arranged.On substrate 2, led chip 7 is arranged across etchant resist 3 laminations.Outer peripheral edges at led chip 7 lower surface 7a are provided with terminal 8a, 8b.Terminal 8a, 8b are electrically connected with electrode 4a, 4b through scolding tin 9a, 9b.Can be electrically connected to led chip 7 supply capabilities through this.
Below, the present invention will be described to enumerate specific embodiment of the present invention and comparative example.The present invention is not limited to following embodiment.
In embodiment and comparative example, the material 1 below using) ~ 18).
1) XPA 1 (having the XPA 1 that obtains in the polymerizable polymer, following synthetic routine 1 of carboxyl)
(synthetic example 1)
In the flask that possesses TM, stirrer, tap funnel and reflux exchanger, add as the ethyl carbitol acetic ester of solvent with as the Diisopropyl azodicarboxylate of catalyzer; Under nitrogen atmosphere, be heated to 80 ℃, dripped the monomer that mixed in molar ratio methacryloxyethyl acid and TEB 3K with 30:70 form through 2 hours.After the dropping, stirred 1 hour, be warming up to 120 ℃.Then, cool off.Add glycidyl acrylate; Its molar weight is 10 with respect to the ratio of the integral molar quantity of the total monomer units of the resin that obtains; Use Tetrabutylammonium bromide as catalyzer, heated 30 hours down, make glycidyl acrylate and carboxyl carry out addition reaction at 100 ℃.After the cooling, from flask, take out, obtain comprising the solution of the resin that contains carboxyl of solids component acid number 60mgKOH/g, the weight-average molecular weight 15000 of 50 weight % (nonvolatile component), two key equivalents 1000.Below, this solution is called XPA 1.
2) XPA 2 (having resulting XPA 2 in the polymerizable polymer, following synthetic routine 2 of carboxyl)
(synthetic example 2)
In ethyl carbitol acetic ester 139 weight parts; Use dimethyl benzyl amine 0.5 weight part as catalyzer, use quinhydrones 0.1 weight part as stopper; Cresols phenol aldehyde type epoxy resin (" Epotohto YDCN-704 ", chemical company of Nippon Steel system) 210 weight parts, vinylformic acid 50 weight parts and acetic acid 18 weight parts of 80 ℃ of epoxy equivalent (weight)s 210, softening temperature are reacted, obtain epoxy acrylate.Epoxy acrylate 278 weight parts and Tetra Hydro Phthalic Anhydride 46 weight parts (hydroxyl with respect to epoxy acrylate is 0.3 mole for 1.0 moles) that obtain are reacted, and the solids component acid number that obtains comprising 65 weight % (nonvolatile component) is the solution of the resin that contains carboxyl with aromatic nucleus of 52mgKOH/g.Below, this solution is called XPA 2.
3) DPHA (Acrylic Acid Monomer, dipentaerythritol acrylate, proportion 1.1)
4) TMPTA (Acrylic Acid Monomer, Viscoat 295, proportion 1.1)
5) TPO (it is Photoepolymerizationinitiater initiater, BASF Japanese firm system that optical free radical produces agent)
6) IRGACURE 819 (it is Photoepolymerizationinitiater initiater, BASF Japanese firm system that optical free radical produces agent)
7) 828 (bisphenol A type epoxy resin, Mitsubishi Chemical Ind's system, proportions 1.2)
8) 806 (bisphenol f type epoxy resin, Mitsubishi Chemical Ind's system, proportions 1.2)
9) CR-50 (titanium oxide, the former industry corporate system of stone, utilize the Titanium Dioxide (Rutile) Top grade of chlorine method manufacturing)
10) R-830 (titanium oxide, the former industry corporate system of stone, utilize the Titanium Dioxide (Rutile) Top grade of sulfuric acid process manufacturing)
11) ethyl carbitol acetic ester (glycol ether monoethyl ether acetate, DAICEL chemical company system, above, the proportion 1.0 of moment of dipole 1Debye)
12) Solvesso 150 (over point in petroleum naphtha, Exxon Mobil corporate system, the distillation characteristics is that the final boiling point in 189 ℃ and the distillation characteristics is 210 ℃)
13) Solvesso 100 (over point in petroleum naphtha, Exxon Mobil corporate system, the distillation characteristics is that the final boiling point in 165 ℃ and the distillation characteristics is 174 ℃)
14) DPG monomethyl ether (Japanese emulsifying agent corporate system)
15) dimethyl propylene glycol (Japanese emulsifying agent corporate system, chemical name: the DPG dme)
16) diethylammonium glycol ether (diethyl diglycol) (Japanese emulsifying agent corporate system, chemical name: the glycol ether diethyl ether)
17) Solvesso 200 (over point in petroleum naphtha, Exxon Mobil corporate system, the distillation characteristics is that the final boiling point in 230 ℃ and the distillation characteristics is 283 ℃)
18) toluene (Exxon Mobil corporate system)
(embodiment 1)
Mix the XPA 1,5g DPHA (dipentaerythritol acrylate), 2g TPO (it is Photoepolymerizationinitiater initiater, BASF Japanese firm system that optical free radical produces agent), 40gCR-50 (titanium oxide, the former industry corporate system of stone) and the 25g Solvesso 150 (petroleum naphtha, Exxon Mobil corporate system) that obtain in the synthetic example 1 of 15g; After mixing 3 minutes with mixing machine (practice too youth SP-500, THINKY corporate system); Mix with three-roller, obtain mixture.Then, use SP-500 that the mixture that obtains is carried out deaeration in 3 minutes, obtain first liquid thus.
828 (bisphenol A type epoxy resin, the Mitsubishi Chemical Ind's systems) and the 5g ethyl carbitol acetic ester (glycol ether monoethyl ether acetate, DAICEL chemical company system) that cooperate 8g; After mixing 3 minutes with mixing machine (practice too youth SP-500, THINKY corporate system); Mix with three-roller, obtain mixture.Then, use SP-500 that the mixture that obtains is carried out deaeration in 3 minutes, obtain second liquid thus.
As above prepare to have two liquid mixed type photosensitive composites of first, second liquid.
(embodiment 2 ~ 49/ reference examples 1 ~ 11 and comparative example 1 ~ 19)
The kind of the material that will in first liquid and second liquid, use and use level that kind shown in below table 1 ~ 8 change; In addition, likewise obtain having first, second liquid (photosensitive composite before mixing) of two liquid mixed types of first, second liquid with embodiment 1.
(evaluation)
The Combination of two liquid:
First liquid and second liquid are put into the round plastic containers (the nearly system BHS-1200 of Ji Vessel Inc) of 1L, utilize the automatic ink mixing machine of Mesh corporate system to stir 10 seconds, make erosion resistant (mixed photosensitive composite) with 50rpm.First liquid and second liquid are put into the round plastic containers (the nearly system BHS-1200 of Ji Vessel Inc) of 1L, utilize Mesh corporate system automatic ink mixing machine to stir 20 seconds, make erosion resistant (mixed photosensitive composite) with 50rpm.First liquid and second liquid are put into the round plastic containers (the nearly system BHS-1200 of Ji Vessel Inc) of 1L, utilize Mesh corporate system automatic ink mixing machine to stir 1 minute, make erosion resistant (mixed photosensitive composite) with 50rpm.
In addition, first liquid and second liquid are put into the round plastic containers (the nearly system BHS-1200 of Ji Vessel Inc) of 1L, utilize Mesh corporate system automatic ink mixing machine to stir 5 minutes, make erosion resistant (mixed photosensitive composite) with 50rpm.
In addition, prepare to be pasted with the FR-4 substrate of 100 * 100mm of Copper Foil on the surface.Through the erosion resistant of silk screen printing after coating on the face that is pasted with Copper Foil of above-mentioned FR-4 substrate has just been stirred, form the erosion resistant layer.Outward appearance through the erosion resistant layer on the visual inspection substrate.
With following determinating reference the Combination of first, second liquid is judged.
[the blended determinating reference of first, second liquid]
A: the erosion resistant after use stirring 10 seconds, stir erosion resistant after 20 seconds, under any one the situation in the erosion resistant after stirring the erosion resistant after 1 minute and stirring 5 minutes, the erosion resistant layer all is uniform.
B: under the situation of using the erosion resistant after stirring 10 seconds; In the erosion resistant layer, find the inequality of the striated of pettiness; But under the situation of the erosion resistant after use stirring 20 seconds, the erosion resistant after stirring the erosion resistant after 1 minute and stirring 5 minutes, the erosion resistant layer is even.
C: under the situation of the erosion resistant after using the erosion resistant after stirring 10 seconds and stirring 20 seconds; In the erosion resistant layer, find the inequality of the striated of pettiness; But under the situation of the erosion resistant after using the erosion resistant after stirring 1 minute and stirring 5 minutes, the erosion resistant layer is even.
D: under the situation of the erosion resistant after use stirring 10 seconds, the erosion resistant after stirring the erosion resistant after 20 seconds and stirring 1 minute; In the erosion resistant layer, find the inequality of the striated of pettiness; But under the situation of using the erosion resistant after stirring 5 minutes, the erosion resistant layer is even.
E: the erosion resistant after use stirring 10 seconds, stir erosion resistant after 20 seconds, under any one the situation in the erosion resistant after stirring the erosion resistant after 1 minute and stirring 5 minutes, in the erosion resistant layer, all find the inequality of striated.
The result is shown in below table 1 ~ 8.In below table 1 ~ 8, " (1) " expression first liquid in the classification of the liquid that is cooperated, " (2) " expression second liquid.
In addition, after the Combination of above-mentioned first, second liquid estimated, can obtain etchant resist through erosion resistant layer on the substrate is solidified.
Need to prove,, compare that embodiment 5 and embodiment 29 can mix photosensitive composite equably in the further short time with embodiment 33 though the blended evaluation result of two liquid of embodiment 5, embodiment 29 and embodiment 33 is " A ".Though the blended evaluation result of two liquid of embodiment 30, embodiment 31 and embodiment 34 is " A ", compare with embodiment 34, embodiment 30 and embodiment 31 can mix photosensitive composite equably in the further short time.Though the blended evaluation result of two liquid of embodiment 35, embodiment 37 and embodiment 39 is " A ", compare with embodiment 39, embodiment 35 and embodiment 37 can mix photosensitive composite equably in the further short time.
Claims (21)
1. first, second liquid of a liquid mixed type, it is used to obtain the photosensitive composite as mixture, and first, second liquid of this two liquid mixed type is for mixing the liquid before this first, second liquid, wherein,
Being mixed with said first, second mixtures of liquids is that photosensitive composite integral body comprises: have polymerizable polymer, the Photoepolymerizationinitiater initiater of carboxyl, compound, titanium oxide and organic solvent with ring-type ether,
In the said photosensitive composite; As said organic solvent; Comprising the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least two kinds in the petroleum naphtha below 290 ℃
Said first liquid comprises said polymerizable polymer; And comprising the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least a part as said organic solvent in the petroleum naphtha below 290 ℃
Said second liquid comprises said compound with ring-type ether; And comprising the over point that is selected from glycol ether monoethyl ether acetate, DPG monomethyl ether and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least a part as said organic solvent in the petroleum naphtha below 220 ℃
Said first liquid comprises said Photoepolymerizationinitiater initiater or comprises said titanium oxide or comprise said Photoepolymerizationinitiater initiater and said titanium oxide,
Do not comprise under the situation of said Photoepolymerizationinitiater initiater at said first liquid, said second liquid comprises said Photoepolymerizationinitiater initiater, does not comprise under the situation of said titanium oxide at said first liquid, and said second liquid comprises said titanium oxide.
2. first, second liquid of two liquid mixed types according to claim 1; Wherein, to comprise the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics be more than 150 ℃ to said first liquid and the final boiling point in the distillation characteristics is at least two kinds of parts as said organic solvent in the petroleum naphtha below 290 ℃.
3. first, second liquid of two liquid mixed types according to claim 1; Wherein, said first liquid comprises DPG monomethyl ether and glycol ether monoethyl ether acetate at least as the part of said organic solvent or to comprise over point in glycol ether monoethyl ether acetate and the distillation characteristics at least be more than 150 ℃ and the final boiling point in the distillation characteristics is that petroleum naphtha below 290 ℃ is as the part of said organic solvent.
4. first, second liquid of two liquid mixed types according to claim 1; Wherein, to comprise the over point in DPG monomethyl ether and the distillation characteristics at least be more than 150 ℃ to said first liquid and the final boiling point in the distillation characteristics is that petroleum naphtha below 290 ℃ is as the part of organic solvent.
5. first, second liquid of two liquid mixed types according to claim 1; Wherein, To comprise the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics in the said photosensitive composite be more than 150 ℃ and the final boiling point in the distillation characteristics is that in the petroleum naphtha below 220 ℃ at least two kinds are as said organic solvent
Comprising the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics in said first liquid is more than 150 ℃ and the final boiling point in the distillation characteristics is at least two kinds of parts as said organic solvent in the petroleum naphtha below 220 ℃.
6. first, second liquid of two liquid mixed types according to claim 1; Wherein, It is more than 150 ℃ that said photosensitive composite comprises the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is that in the petroleum naphtha below 220 ℃ at least two kinds are as said organic solvent
Said first liquid comprises DPG monomethyl ether, the glycol ether monoethyl ether acetate part as said organic solvent, or to comprise over point in glycol ether monoethyl ether acetate and the distillation characteristics at least be more than 150 ℃ and the final boiling point in the distillation characteristics is that petroleum naphtha below 220 ℃ is as the part of said organic solvent.
7. first, second liquid of two liquid mixed types according to claim 1; Wherein, It is more than 150 ℃ that said photosensitive composite comprises the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is that in the petroleum naphtha below 220 ℃ at least two kinds are as said organic solvent
It is more than 150 ℃ that said first liquid comprises over point in DPG monomethyl ether and the distillation characteristics at least and the final boiling point in the distillation characteristics is that petroleum naphtha below 220 ℃ is as the part of said organic solvent.
8. according to first, second liquid of each described two liquid mixed types in the claim 1 ~ 7, wherein, said first liquid comprises said Photoepolymerizationinitiater initiater.
9. according to first, second liquid of each described two liquid mixed types in the claim 1 ~ 7, wherein, said first liquid comprises said titanium oxide.
10. according to first, second liquid of each described two liquid mixed types in the claim 1 ~ 7, wherein, said first liquid comprises said Photoepolymerizationinitiater initiater and said titanium oxide.
11. according to first, second liquid of each described two liquid mixed types in the claim 1 ~ 7, wherein, the photosensitive composite that is mixed with said first, second liquid is the solder resist compsn.
12. the method for manufacture of a printed wiring board, this printed wiring board possess the printed wiring board main body that has circuit on the surface, the lip-deep soldering-resistance layer that is provided with circuit that is stacked in this printed wiring board main body,
This method comprises following operation:
Mix first, second liquid, the solder resist compsn that obtains being mixed with said first, second liquid is the operation of photosensitive composite;
Have on the surface on the surface that is provided with circuit of printed wiring board main body of circuit; It is photosensitive composite that coating mixed has the solder resist compsn of said first, second liquid; Formation is stacked in the operation of the lip-deep soldering-resistance layer that is provided with said circuit of said printed wiring board main body
The solder resist compsn that is mixed with said first, second liquid is that photosensitive composite integral body comprises polymerizable polymer, the Photoepolymerizationinitiater initiater with carboxyl, the compound with ring-type ether, titanium oxide and organic solvent,
It is more than 150 ℃ that said photosensitive composite comprises the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is that in the petroleum naphtha below 290 ℃ at least two kinds are as said organic solvent
Said first liquid comprises said polymerizable polymer; And comprising the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least a part as said organic solvent in the petroleum naphtha below 290 ℃
Said second liquid comprises said compound with ring-type ether; And comprising the over point that is selected from glycol ether monoethyl ether acetate, DPG monomethyl ether and the distillation characteristics is more than 150 ℃ and the final boiling point in the distillation characteristics is at least a part as said organic solvent in the petroleum naphtha below 220 ℃
Said first liquid comprises said Photoepolymerizationinitiater initiater or comprises said titanium oxide or comprise said Photoepolymerizationinitiater initiater and said titanium oxide,
Do not comprise under the situation of said Photoepolymerizationinitiater initiater at said first liquid, said second liquid comprises said Photoepolymerizationinitiater initiater, does not comprise under the situation of said titanium oxide at said first liquid, and said second liquid comprises said titanium oxide.
13. the method for manufacture of printed wiring board according to claim 12; Wherein, to comprise the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics in said first liquid be more than 150 ℃ and the final boiling point in the distillation characteristics is at least two kinds of parts as said organic solvent in the petroleum naphtha below 290 ℃.
14. the method for manufacture of printed wiring board according to claim 12; Wherein, to comprise DPG monomethyl ether and glycol ether monoethyl ether acetate at least or comprise over point in glycol ether monoethyl ether acetate and the distillation characteristics at least be more than 150 ℃ and the final boiling point in the distillation characteristics is that petroleum naphtha below 290 ℃ is as the part of said organic solvent to said first liquid.
15. the method for manufacture of printed wiring board according to claim 12; Wherein, to comprise the over point in DPG monomethyl ether and the distillation characteristics at least be more than 150 ℃ to said first liquid and the final boiling point in the distillation characteristics is that petroleum naphtha below 290 ℃ is as the part of said organic solvent.
16. the method for manufacture of printed wiring board according to claim 12; Wherein, It is more than 150 ℃ that said photosensitive composite comprises the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is that in the petroleum naphtha below 220 ℃ at least two kinds are as said organic solvent
Comprising the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics in said first liquid is more than 150 ℃ and the final boiling point in the distillation characteristics is at least two kinds of parts as said organic solvent in the petroleum naphtha below 220 ℃.
17. the method for manufacture of printed wiring board according to claim 12; Wherein, It is more than 150 ℃ that said photosensitive composite comprises the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is that in the petroleum naphtha below 220 ℃ at least two kinds are as said organic solvent
Said first liquid comprises DPG monomethyl ether and glycol ether monoethyl ether acetate at least as the part of said organic solvent or to comprise over point in glycol ether monoethyl ether acetate and the distillation characteristics at least be more than 150 ℃ and the final boiling point in the distillation characteristics is that petroleum naphtha below 220 ℃ is as the part of said organic solvent.
18. the method for manufacture of printed wiring board according to claim 12; Wherein, It is more than 150 ℃ that said photosensitive composite comprises the over point that is selected from DPG monomethyl ether, glycol ether monoethyl ether acetate and the distillation characteristics and the final boiling point in the distillation characteristics is that in the petroleum naphtha below 220 ℃ at least two kinds are as said organic solvent
It is more than 150 ℃ that said first liquid comprises over point in DPG monomethyl ether and the distillation characteristics at least and the final boiling point in the distillation characteristics is that petroleum naphtha below 220 ℃ is as the part of said organic solvent.
19. according to the method for manufacture of each described printed wiring board in the claim 12 ~ 18, wherein, said first liquid comprises said Photoepolymerizationinitiater initiater.
20. according to the method for manufacture of each described printed wiring board in the claim 12 ~ 18, wherein, said first liquid comprises said titanium oxide.
21. according to the method for manufacture of each described printed wiring board in the claim 12 ~ 18, wherein, said first liquid comprises said Photoepolymerizationinitiater initiater and said titanium oxide.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-028924 | 2011-02-14 | ||
| JP2011028924 | 2011-02-14 | ||
| JP2011-092713 | 2011-04-19 | ||
| JP2011092713A JP4850313B1 (en) | 2011-02-14 | 2011-04-19 | Two-liquid mixed type first and second liquid and method for producing printed wiring board |
| JP2011-092714 | 2011-04-19 | ||
| JP2011092714 | 2011-04-19 | ||
| JP2011200946 | 2011-09-14 | ||
| JP2011-200946 | 2011-09-14 | ||
| PCT/JP2012/050105 WO2012111356A1 (en) | 2011-02-14 | 2012-01-05 | Two-liquid mixing first and second liquids and method for producing printed circuit board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102762627A true CN102762627A (en) | 2012-10-31 |
| CN102762627B CN102762627B (en) | 2014-03-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280000309.XA Active CN102762627B (en) | 2011-02-14 | 2012-01-05 | Two-liquid mixing first and second liquids and method for producing printed circuit board |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR101250736B1 (en) |
| CN (1) | CN102762627B (en) |
| TW (1) | TWI506358B (en) |
| WO (1) | WO2012111356A1 (en) |
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| CN106019828A (en) * | 2015-03-25 | 2016-10-12 | 积水化学工业株式会社 | First liquid and second liquid of two-liquid mixing type and method for manufacturing printed wiring board |
| CN106019827A (en) * | 2015-03-25 | 2016-10-12 | 积水化学工业株式会社 | First liquid and second liquid of two-liquid mixing type and method for manufacturing printed wiring board |
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI506358B (en) | 2015-11-01 |
| WO2012111356A1 (en) | 2012-08-23 |
| KR20120109513A (en) | 2012-10-08 |
| CN102762627B (en) | 2014-03-26 |
| TW201239519A (en) | 2012-10-01 |
| KR101250736B1 (en) | 2013-04-03 |
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Effective date of registration: 20240117 Address after: Saitama Prefecture, Japan Patentee after: TAIYO HOLDINGS Co.,Ltd. Address before: Osaka, Japan Patentee before: SEKISUI CHEMICAL Co.,Ltd. |