JP2005157048A - Photosensitive resin composition, composition for solder resist, photosensitive dry film and printed wiring board - Google Patents
Photosensitive resin composition, composition for solder resist, photosensitive dry film and printed wiring board Download PDFInfo
- Publication number
- JP2005157048A JP2005157048A JP2003396958A JP2003396958A JP2005157048A JP 2005157048 A JP2005157048 A JP 2005157048A JP 2003396958 A JP2003396958 A JP 2003396958A JP 2003396958 A JP2003396958 A JP 2003396958A JP 2005157048 A JP2005157048 A JP 2005157048A
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- JP
- Japan
- Prior art keywords
- epoxy
- composition
- resin
- acid
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims description 31
- 229910000679 solder Inorganic materials 0.000 title claims description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 67
- 239000003822 epoxy resin Substances 0.000 claims abstract description 63
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 41
- 239000003085 diluting agent Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 44
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000000576 coating method Methods 0.000 abstract description 50
- 239000011248 coating agent Substances 0.000 abstract description 47
- 230000035945 sensitivity Effects 0.000 abstract description 17
- 238000011161 development Methods 0.000 abstract description 12
- 239000003513 alkali Substances 0.000 abstract description 8
- 238000003848 UV Light-Curing Methods 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 36
- -1 bisphenol A type Chemical compound 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 26
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 18
- 150000007519 polyprotic acids Polymers 0.000 description 18
- 239000000758 substrate Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 125000003700 epoxy group Chemical group 0.000 description 12
- 229920003986 novolac Polymers 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000005476 soldering Methods 0.000 description 11
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 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 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- 230000036211 photosensitivity Effects 0.000 description 5
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- SOEZXSYRGLWFQV-UHFFFAOYSA-N 2-methyl-4-[1,2,2-tris(4-hydroxy-3-methylphenyl)ethyl]phenol Chemical compound C1=C(O)C(C)=CC(C(C(C=2C=C(C)C(O)=CC=2)C=2C=C(C)C(O)=CC=2)C=2C=C(C)C(O)=CC=2)=C1 SOEZXSYRGLWFQV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000011417 postcuring Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZJUVPYQIOGVRKO-UHFFFAOYSA-N 2,6-dimethyl-4-[1,2,2-tris(4-hydroxy-3,5-dimethylphenyl)ethyl]phenol Chemical compound CC1=C(O)C(C)=CC(C(C(C=2C=C(C)C(O)=C(C)C=2)C=2C=C(C)C(O)=C(C)C=2)C=2C=C(C)C(O)=C(C)C=2)=C1 ZJUVPYQIOGVRKO-UHFFFAOYSA-N 0.000 description 3
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012916 structural analysis Methods 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 238000010292 electrical insulation Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
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- 150000002576 ketones Chemical class 0.000 description 2
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- 239000012528 membrane Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
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- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Materials For Photolithography (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は、紫外線露光及び希アルカリ水溶液による現像で画像形成可能であり、タック性（指触乾燥性）、感度、熱管理幅、耐熱性に優れ、その他の塗膜性能も良好な活性エネルギー線感光性樹脂組成物に関するものである。 The present invention can form an image by ultraviolet exposure and development with a dilute alkaline aqueous solution, and has excellent tackiness (touch-drying property), sensitivity, thermal management width, heat resistance, and other active energy rays with excellent coating performance. The present invention relates to a photosensitive resin composition.
エポキシアクリレート樹脂を含め、アクリレートオリゴマー類はその光硬化特性が優れている事から、広く産業界に応用されている。その中でもエポキシアクリレート樹脂は、光硬化性と共に密着性、耐熱性、耐薬品性が他のアクリレートオリゴマー類に比べて優れているため、金属コーティングやプリント配線板のソルダーレジストの塗膜の主要成分として広く利用されてきた。例えばプリント配線板は、基板の上に導体回路のパターンを形成し、そのパターンのはんだ付けランドに電子部品をはんだ付けすることにより搭載するためのものであり、そのはんだ付けランドを除く回路部分は永久保護皮膜としてのソルダーレジスト膜で被覆される。これにより、プリント配線板に電子部品をはんだ付けする際にはんだが不必要な部分に付着するのを防止すると共に、回路導体が空気に直接曝されて酸化や湿度により腐食されるのを防止する。従来、ソルダーレジスト膜は、基板上にその溶液組成物をスクリーン印刷法でパターン形成し、溶剤を除く乾燥をした後、紫外線または熱により硬化させることが主流とされてきた。 Acrylate oligomers, including epoxy acrylate resins, are widely applied to industry because of their excellent photocuring properties. Among them, epoxy acrylate resin is superior to other acrylate oligomers in terms of adhesion, heat resistance, and chemical resistance as well as photocuring properties, so it is a major component of solder coatings for metal coatings and printed wiring boards. It has been widely used. For example, a printed wiring board is for mounting by forming a pattern of a conductor circuit on a substrate and soldering an electronic component to the soldering land of the pattern, and the circuit portion excluding the soldering land is It is covered with a solder resist film as a permanent protective film. This prevents solder from adhering to unnecessary parts when soldering electronic components to a printed wiring board, and prevents circuit conductors from being directly exposed to air and being corroded by oxidation or humidity. . Conventionally, a solder resist film has been mainly formed by patterning a solution composition on a substrate by a screen printing method, drying the solvent composition, and then curing it with ultraviolet rays or heat.
ところが、最近、プリント配線基板の配線密度の向上（細密化）の要求にともないソルダーレジスト組成物（ソルダーレジストインキ組成物ともいう）も高解像性、高精度化が要求され、民生用基板、産業用基板を問わずスクリーン印刷法から、位置精度、導体エッジ部の被覆性に優れる液状フォトソルダーレジスト法（写真現像法）が提案されている。例えば特許文献１、特許文献２には、ビスフェノール型エポキシアクリレート、増感剤、エポキシ化合物、エポキシ硬化剤などからなるソルダーレジスト組成物が開示されている。これらのソルダーレジスト組成物は、プリント配線板上に感光性樹脂組成物である液状組成物を全面塗布し、溶媒を揮発させた後、露光して未露光部分を有機溶剤を用いて除去し、現像するものである。しかし、この有機溶剤による未露光部分の除去（現像）は、有機溶剤を多量に使用するため、環境汚染や火災などの危険性があるのみならず、環境汚染の問題があり、特に人体に与える影響が最近大きくクローズアップされてきていることから、その対策に苦慮しているのが現状である。
これらの問題を解決するために、希アルカリ水溶液で現像可能なアルカリ現像型フォトソルダーレジスト組成物が提案されている。例えば特許文献３、特許文献４には、エポキシ樹脂に不飽和モノカルボン酸を反応させ、更に多塩基酸無水物を付加させた反応生成物をベースポリマーとする材料が開示されている。また、特許文献５には、ノボラック型エポキシ樹脂と不飽和モノカルボン酸との反応物と、飽和または不飽和多塩基酸無水物とを反応せしめて得られる活性エネルギー線硬化性樹脂と、光重合開始剤を含有する希アルカリ水溶液により現像可能な光硬化性の液状レジストインキ組成物が開示されている。
これらの液状ソルダーレジスト組成物は、エポキシアクリレートにカルボキシル基を導入することによって、感光性や希アルカリ水溶液での現像性を付与させたものである。しかし、この組成物にはさらに、その塗膜を露光、現像処理して所望のレジストパターンを形成したあと、通常熱硬化させるために、熱硬化成分として、一般的にエポキシ化合物を含有させ、上記エポキシアクリレートに導入したカルボキシル基とを反応させる加熱処理を行い、密着性、硬度、耐熱性、電気絶縁性などに優れるレジスト膜を形成させている。この場合、一般的にはエポキシ樹脂とともに、エポキシ樹脂用硬化剤が併用される。 These liquid solder resist compositions are provided with photosensitivity and developability in a dilute alkaline aqueous solution by introducing a carboxyl group into epoxy acrylate. However, this composition further contains an epoxy compound as a thermosetting component in order to normally heat-cure after the coating film is exposed and developed to form a desired resist pattern, A heat treatment for reacting the carboxyl group introduced into the epoxy acrylate is performed to form a resist film having excellent adhesion, hardness, heat resistance, electrical insulation and the like. In this case, generally, an epoxy resin curing agent is used together with the epoxy resin.
しかしながら、このようなソルダーレジストにおいて、近年のプリント配線板の高密度化から精細なパターニングが要求され、薄膜化が必要になっていることや、実装材料の鉛フリー化などから、より高い耐熱性が要求されるようになってきている。 However, in such solder resists, finer patterning is required due to the recent increase in the density of printed wiring boards, and it is necessary to reduce the thickness, and lead-free mounting materials. Is becoming required.
耐熱性向上のため、上記ソルダーレジスト組成物において、上記の熱硬化成分として、熱硬化樹脂の添加量を増やしたり、反応性の良い熱硬化樹脂を用いたりしても、熱管理幅が低下しソルダーレジスト組成物の設計が行い難いという問題がある。 In order to improve heat resistance, in the above solder resist composition, even if the amount of thermosetting resin added is increased as the above thermosetting component or a highly reactive thermosetting resin is used, the thermal management width decreases. There is a problem that it is difficult to design a solder resist composition.
本発明の課題は、紫外線露光及び希アルカリ水溶液による現像により画像形成可能であり、タック性（指触乾燥性）、感度、熱管理幅、耐熱性に優れ、その他の塗膜性能も良好な感光性樹脂組成物を提供することである。 The problem of the present invention is that it can form an image by ultraviolet exposure and development with a dilute aqueous alkali solution, and is excellent in tackiness (dryness to touch), sensitivity, thermal management width, heat resistance, and other coating performance. It is providing a functional resin composition.
本発明者らは、上記目的を達成するために鋭意研究した結果、（Ａ）紫外線硬化性樹脂、（Ｂ）光重合開始剤、（Ｃ）希釈剤および（Ｄ）熱硬化性成分を含有する感光性樹脂組成物であって、（Ｄ）前記熱硬化性成分が式（１）で表される高軟化点エポキシ樹脂を含む感光性樹脂組成物は、塗膜の耐熱性を格段に向上させることができることを見出し、特にプリント配線板製造用ソルダーレジスト用として好適な硬化膜を提供することを見出し、本発明をするに至った。
本発明において、（Ａ）紫外線硬化性樹脂とは、例えば１分子中にエポキシ基を少なくとも２個有する多官能エポキシ樹脂のエポキシ基の少なくとも一部にアクリル酸又はメタクリル酸等のラジカル重合性不飽和モノカルボン酸を反応させた後、生成した水酸基に多塩基酸又はその無水物を反応させたものなどを挙げることができる。 In the present invention, (A) the ultraviolet curable resin is, for example, a radical polymerizable unsaturated such as acrylic acid or methacrylic acid in at least a part of the epoxy group of a polyfunctional epoxy resin having at least two epoxy groups in one molecule. Examples thereof include a product obtained by reacting a monocarboxylic acid and then reacting a polybasic acid or an anhydride thereof with the generated hydroxyl group.
上記の多官能のエポキシ化合物としては、少なくとも２官能のエポキシ樹脂であればいずれでも使用可能であり、エポキシ当量に制限は特にないが、通常１，０００以下、好ましくは１００〜５００のものを用いる。例えば、ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＡＤ型等のフェノールノボラック型エポキシ樹脂、ｏ−クレゾールノボラック型等のクレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、環状脂肪族多官能エポキシ樹脂、グリシジルエステル型多官能エポキシ樹脂、グリシジルアミン型多官能エポキシ樹脂有、複素環式多官能エポキシ樹脂、ビスフェノール変性ノボラック型エポキシ樹脂、多官能変性ノボラック型エポキシ樹脂、フェノール類とフェノール性水酸基を有する芳香族アルデヒドとの縮合物型エポキシ樹脂等を挙げることができる。また、これらの樹脂にＢｒ、Ｃｌ等のハロゲン原子を導入したものなども挙げられる。これらの内でも耐熱性を考慮すると、ノボラック型エポキシ樹脂が好ましい。これらのエポキシ樹脂は単独で用いてもよく、また２種以上を併用してもよい。 As the polyfunctional epoxy compound, any epoxy resin can be used as long as it is at least bifunctional, and the epoxy equivalent is not particularly limited, but usually 1,000 or less, preferably 100 to 500 is used. . For example, phenol novolac type epoxy resins such as bisphenol A type, bisphenol F type and bisphenol AD type, cresol novolac type epoxy resins such as o-cresol novolak type, bisphenol A novolac type epoxy resin, cycloaliphatic polyfunctional epoxy resin, glycidyl Ester type polyfunctional epoxy resin, Glycidylamine type polyfunctional epoxy resin, Heterocyclic polyfunctional epoxy resin, Bisphenol modified novolac type epoxy resin, Multifunctional modified novolak type epoxy resin, Aromatic aldehyde having phenols and phenolic hydroxyl group And a condensate type epoxy resin. Further, those obtained by introducing halogen atoms such as Br and Cl into these resins are also included. Among these, considering heat resistance, novolac type epoxy resin is preferable. These epoxy resins may be used alone or in combination of two or more.
これらのエポキシ系化合物とラジカル重合性不飽和モノカルボン酸を反応させると、エポキシ基とカルボキシル基の反応によりエポキシ基が開裂し、水酸基とエステル結合が生成する。使用するラジカル重合性不飽和モノカルボン酸としては、特に制限は無く、例えばアクリル酸、メタクリル酸、クロトン酸、桂皮酸などがあるが、アクリル酸及びメタクリル酸の少なくとも一方（以下、（メタ）アクリル酸ということがある。）が好ましく、特にアクリル酸が好ましい。エポキシ系化合物とラジカル重合性不飽和モノカルボン酸との反応方法に特に制限は無く、例えばエポキシ系化合物とアクリル酸を適当な希釈剤中で加熱することにより反応できる。希釈剤としては、例えば、メチルエチルケトン、シクロヘキサノン等のケトン類、トルエン、キシレン等の芳香族炭化水素類、メタノール、イソプロパノール、シクロヘキサノール、などのアルコール類、シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類、石油エーテル、石油ナフサ等の石油系溶剤類、セロソルブ、ブチルセロソルブ等のセロソルブ類、カルビトール、ブチルカルビトール等のカルビトール類、酢酸エチル、酢酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート等の酢酸エステル類等を挙げることができる。また触媒としては、例えば、トリエチルアミン、トリブチルアミンなどのアミン類、トリフェニルホスフィン、トリフェニルホスフェートなどのリン化合物類等を挙げることができる。 When these epoxy compounds and a radically polymerizable unsaturated monocarboxylic acid are reacted, the epoxy group is cleaved by the reaction of the epoxy group and the carboxyl group, and a hydroxyl group and an ester bond are generated. The radical polymerizable unsaturated monocarboxylic acid to be used is not particularly limited and includes, for example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc., but at least one of acrylic acid and methacrylic acid (hereinafter referred to as (meth) acrylic). It is sometimes referred to as an acid.), And acrylic acid is particularly preferable. There is no restriction | limiting in particular in the reaction method of an epoxy-type compound and radically polymerizable unsaturated monocarboxylic acid, For example, it can react by heating an epoxy-type compound and acrylic acid in a suitable diluent. Examples of the diluent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol and cyclohexanol, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Petroleum solvents such as petroleum ether and petroleum naphtha, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl Examples include acetates such as carbitol acetate. Examples of the catalyst include amines such as triethylamine and tributylamine, and phosphorus compounds such as triphenylphosphine and triphenylphosphate.
上記のエポキシ系化合物とラジカル重合性不飽和モノカルボン酸の反応において、このエポキシ系化合物としては１分子中に２個以上のエポキシ基を有するエポキシ系化合物を用いるが、その少なくとも２個のエポキシ基にラジカル重合性不飽和モノカルボン酸を反応させる。これにより後述の飽和もしくは不飽和の多塩基酸またはその多塩基酸無水物を反応させることにより、少なくとも二塩基性のエポキシ系化合物変性不飽和多塩基酸を得ることができる。エポキシ系化合物が二官能のときは、エポキシ系化合物が有するエポキシ基１当量あたりラジカル重合性不飽和モノカルボン酸１当量反応させる。エポキシ系化合物が３官能以上のときは、エポキシ系化合物が有するエポキシ基１当量あたりラジカル重合性不飽和モノカルボン酸を０．７〜１．２当量反応させることが好ましく、アクリル酸またはメタクリル酸の少なくとも一方を用いるときは、さらに好ましくは０．８〜１．０当量加えて反応させる。ラジカル重合性不飽和モノカルボン酸が０．７当量未満であると、後続の合成の合成反応時にゲル化を起こすことがあったり、あるいは樹脂の安定性が低下する。またラジカル重合性不飽和モノカルボン酸が過剰であると未反応のカルボン酸が多く残存するため、硬化物の諸特性（例えば耐水性等）を低下させる恐れがある。 In the reaction between the epoxy compound and the radical polymerizable unsaturated monocarboxylic acid, an epoxy compound having two or more epoxy groups in one molecule is used as the epoxy compound, and at least two epoxy groups are used. Is reacted with a radically polymerizable unsaturated monocarboxylic acid. Thus, at least a dibasic epoxy compound-modified unsaturated polybasic acid can be obtained by reacting a saturated or unsaturated polybasic acid or a polybasic acid anhydride thereof described later. When the epoxy compound is difunctional, 1 equivalent of radically polymerizable unsaturated monocarboxylic acid is reacted per 1 equivalent of epoxy group of the epoxy compound. When the epoxy compound has three or more functional groups, it is preferable to react 0.7 to 1.2 equivalents of radically polymerizable unsaturated monocarboxylic acid per equivalent of epoxy group of the epoxy compound. When at least one is used, more preferably 0.8 to 1.0 equivalent is added and reacted. When the radically polymerizable unsaturated monocarboxylic acid is less than 0.7 equivalent, gelation may occur during the subsequent synthesis reaction, or the stability of the resin is lowered. If the radically polymerizable unsaturated monocarboxylic acid is excessive, a large amount of unreacted carboxylic acid remains, which may reduce various properties (eg, water resistance) of the cured product.
エポキシ系化合物とラジカル重合性不飽和モノカルボン酸の反応は、加熱状態で行うのが好ましく、その反応温度は、８０〜１４０℃である事が好ましい。反応温度が１４０℃を超えるとラジカル重合性不飽和モノカルボン酸が熱重合を起こし易くなり合成が困難になることがあり、また８０℃未満では反応速度が遅くなり、実際の製造上好ましくないことがある。複数種の上記エポキシ系化合物を用いる場合や、上記エポキシ系化合物を単一種で用いる場合でも、各エポキシ形化合物の個々の分子を結合したい場合には、エポキシ基１モルに対してラジカル重合性不飽和モノカルボン酸を０．４〜０.９モル反応させることが好ましい。エポキシ系化合物とラジカル重合性不飽和モノカルボン酸の希釈剤中での反応においては、希釈剤の配合量が反応系の総重量に対して、２０〜５０％である事が好ましい。エポキシ樹脂とラジカル重合性不飽和モノカルボン酸の反応生成物は単離することなく、希釈剤の溶液のまま、次の多塩基酸類との反応に供する事ができる。 The reaction between the epoxy compound and the radically polymerizable unsaturated monocarboxylic acid is preferably performed in a heated state, and the reaction temperature is preferably 80 to 140 ° C. If the reaction temperature exceeds 140 ° C, the radically polymerizable unsaturated monocarboxylic acid is likely to undergo thermal polymerization and may be difficult to synthesize, and if it is less than 80 ° C, the reaction rate will be slow, which is undesirable in actual production. There is. Even when a plurality of types of the above epoxy compounds are used or when the above epoxy compounds are used as a single type, when it is desired to bond individual molecules of each epoxy type compound, radical polymerizable non-polymerization per mole of epoxy group is not possible. It is preferable to react 0.4 to 0.9 mol of a saturated monocarboxylic acid. In the reaction of the epoxy compound and the radically polymerizable unsaturated monocarboxylic acid in the diluent, the blending amount of the diluent is preferably 20 to 50% with respect to the total weight of the reaction system. The reaction product of the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid can be subjected to the reaction with the next polybasic acid in the form of a diluent without isolation.
上記エポキシ樹脂とラジカル重合性不飽和モノカルボン酸との反応生成物である不飽和モノカルボン酸化エポキシ系化合物に、多塩基酸またはその無水物（これらの両方でも良い）を反応させる。多塩基酸またはその無水物としては、特に制限は無く、飽和、不飽和のいずれも使用できる。このような多塩基酸としては、コハク酸、マレイン酸、アジピン酸、クエン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルテトラヒドロフタル酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、メチルエンドメチレンテトラヒドロフタル酸、トリメリット酸、ピロメリット酸及びジグリコール酸等が挙げられ、多塩基酸無水物としてはこれらの無水物が挙げられる。これらの化合物は単独で使用することができ、また２種以上を混合してもよい。多塩基酸又は多塩基酸無水物は、上記のエポキシ樹脂とラジカル重合性不飽和モノカルボン酸との反応で生成した水酸基に反応し、樹脂に遊離させたカルボキシル基を持たせる。反応させようとする多塩基酸の使用量は、エポキシ樹脂とラジカル重合性不飽和モノカルボン酸との反応生成物が有する水酸基１モルに対し０．２〜１．０モルである事が望ましい。露光時に高感度の樹脂膜が得られる点からは、好ましくは０．３〜０．９モル、さらに好ましくは０．４〜０．８モルの割合で反応させる。０．２モル未満であると、得られた樹脂の希アルカリ現像性が低下することがあり、また１．０モルを超えると最終的に得られる硬化塗膜の諸特性（例えば耐水性等）を低下させることがある。多塩基酸は、上記の不飽和モノカルボン酸化エポキシ樹脂に添加され、脱水縮合反応され、反応時生成した水は反応系から連続的に取り出すことが好ましいが、その反応は加熱状態で行うのが好ましく、その反応温度は、７０〜１３０℃である事が好ましい。反応温度が１３０℃を超えると、エポキシ樹脂に結合されたものや、未反応モノマーのラジカル重合性不飽和基が熱重合を起こし易くなり合成が困難になることがあり、また７０℃以下では反応速度が遅くなり、実際の製造上好ましくないことがある。多塩基酸無水物を使用する場合もこれに準ずる。上記の多塩基酸又はその無水物と不飽和モノカルボン酸化エポキシ樹脂との反応生成物である多塩基酸変性不飽和モノカルボン酸化エポキシ樹脂の酸価は、６０〜３００ｍｇＫＯＨ/ｇが好ましい。反応させる多塩基酸又はその無水物の量により、反応生成物の酸価は調整できる。 A polybasic acid or an anhydride thereof (or both of them) may be reacted with an unsaturated monocarboxylic oxide epoxy compound which is a reaction product of the epoxy resin and a radically polymerizable unsaturated monocarboxylic acid. There is no restriction | limiting in particular as a polybasic acid or its anhydride, Either saturated and unsaturated can be used. Such polybasic acids include succinic acid, maleic acid, adipic acid, citric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, Examples thereof include methyl endomethylenetetrahydrophthalic acid, trimellitic acid, pyromellitic acid and diglycolic acid, and polybasic acid anhydrides include these anhydrides. These compounds can be used alone or in combination of two or more. The polybasic acid or polybasic acid anhydride reacts with a hydroxyl group generated by the reaction of the above-described epoxy resin and a radically polymerizable unsaturated monocarboxylic acid, thereby giving the resin a carboxyl group released. The amount of the polybasic acid to be reacted is preferably 0.2 to 1.0 mol with respect to 1 mol of the hydroxyl group of the reaction product of the epoxy resin and the radically polymerizable unsaturated monocarboxylic acid. From the point of obtaining a highly sensitive resin film at the time of exposure, the reaction is preferably carried out at a rate of 0.3 to 0.9 mol, more preferably 0.4 to 0.8 mol. When the amount is less than 0.2 mol, the dilute alkali developability of the obtained resin may be deteriorated. When the amount exceeds 1.0 mol, various properties (for example, water resistance) of the finally obtained cured coating film may be obtained. May be reduced. The polybasic acid is preferably added to the unsaturated monocarboxylic oxide epoxy resin and subjected to a dehydration condensation reaction. The water produced during the reaction is preferably continuously removed from the reaction system, but the reaction is carried out in a heated state. Preferably, the reaction temperature is 70 to 130 ° C. When the reaction temperature exceeds 130 ° C., those bonded to an epoxy resin and radically polymerizable unsaturated groups of unreacted monomers may easily cause thermal polymerization, making synthesis difficult. The speed is slow, which may be undesirable in actual manufacturing. The same applies when polybasic acid anhydrides are used. The acid value of the polybasic acid-modified unsaturated monocarboxylic acid epoxy resin, which is a reaction product of the polybasic acid or anhydride thereof and the unsaturated monocarboxylic acid epoxy resin, is preferably 60 to 300 mgKOH / g. The acid value of the reaction product can be adjusted by the amount of the polybasic acid or anhydride thereof to be reacted.
本発明においては、上記の多塩基酸変性不飽和モノカルボン酸化エポキシ樹脂も感光性樹脂として使用できるが、上記の多塩基酸変性不飽和モノカルボン酸化エポキシ樹脂の有するカルボシキル基の一部に、１つ以上のラジカル重合性不飽和基とエポキシ基を持つグリシジル化合物を反応させることにより、ラジカル重合性不飽和基を更に導入し、更に感光性を向上させた感光性樹脂としても良い。この感光性を向上させた感光性樹脂は、最後のグリシジル化合物の反応によってラジカル重合性不飽和基が、その前駆体の感光性樹脂の高分子の骨格の側鎖に結合するため、光重合反応性が高く、優れた感光特性を持つことができる。１つ以上のラジカル重合性不飽和基とエポキシ基を持つ化合物としては、例えば、グリシジルアクリレート、グリシジルメタクリレート、アリルグリシジルエーテル、ペンタエリスリトールトリアクリレートモノグリシジルエーテル等が挙げられる。なお、グリシジル基は１分子中に複数有していてもよい。これらの化合物は単独で用いてもよく、混合して用いてもよい。上記のグリシジル化合物は、上記の多塩基酸変性不飽和モノカルボン酸化エポキシ樹脂の溶液に添加して反応させるが、その樹脂に導入したカルボキシル基１モルに対し、通常０．０５〜０．５モルの割合で反応させる。得られる感光性樹脂を含有する感光性樹脂組成物の感光性（感度）や、熱管理幅及び電気絶縁性等を考慮すると、好ましくは０．１〜０．５モルの割合で反応させるのが有利である。反応温度は８０〜１２０℃が好ましい。このようにして得られるグリシジル化合物付加多塩基酸変性不飽和モノカルボン酸化エポキシ樹脂からなる感光性樹脂は酸価が４５〜２５０ｍｇＫＯＨ/ｇである事が好ましい。 In the present invention, the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin can also be used as a photosensitive resin. However, a part of the carboxyl group of the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin has 1 It is good also as the photosensitive resin which further introduce | transduced the radically polymerizable unsaturated group and made the photosensitivity improved by making the glycidyl compound which has one or more radically polymerizable unsaturated groups and an epoxy group react. The photosensitive resin with improved photosensitivity has a photopolymerization reaction because the radical polymerizable unsaturated group is bonded to the side chain of the polymer skeleton of the precursor photosensitive resin by the reaction of the last glycidyl compound. It has high properties and can have excellent photosensitivity. Examples of the compound having one or more radically polymerizable unsaturated groups and an epoxy group include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, pentaerythritol triacrylate monoglycidyl ether, and the like. In addition, you may have multiple glycidyl groups in 1 molecule. These compounds may be used alone or in combination. The glycidyl compound is added to the solution of the polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin and reacted. Usually, 0.05 to 0.5 mol per 1 mol of the carboxyl group introduced into the resin. React at a rate of Considering the photosensitivity (sensitivity) of the photosensitive resin composition containing the resulting photosensitive resin, the thermal management width, the electrical insulation, etc., the reaction is preferably carried out at a rate of 0.1 to 0.5 mol. It is advantageous. The reaction temperature is preferably 80 to 120 ° C. The photosensitive resin comprising the glycidyl compound-added polybasic acid-modified unsaturated monocarboxylic oxide epoxy resin thus obtained preferably has an acid value of 45 to 250 mgKOH / g.
本発明においては、上記（Ｂ）光重合開始剤としては、特に制限はなく、従来知られているものはいずれも使用できる。具体的には、代表的なものとしては例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン−ｎ−ブチルエーテル、ベンゾインイソブチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、２, ２- ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、２- ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モルフォリノ−プロパン−１−オン、４−
（２−ヒドロキシエトキシ） フェニル−２−（ヒドロキシ−２− プロピル） ケトン、ベンゾフェノン、ｐ−フェニルベンゾフェノン、４, ４′−ジエチルアミノベンゾフェノン、ジクロルベンゾフェノン、２−メチルアントラキノン、２−エチルアントラキノン、２−
ターシャリーブチルアントラキノン、２−アミノアントラキノン、 ２−メチルチオキサントン、２−エチルチオキサントン、２−クロルチオキサントン、２，４−ジメチルチオキサントン、２，４ジエチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール、Ｐ−ジメチルアミノ安息香酸エチルエステル等が挙げられる。これらを単独または組み合わせて用いることができる。光重合開始剤の使用量は、上記（Ａ）成分の活性化エネルギー線硬化性樹脂１００重量部に対して、通常０．２〜５０重量部である。０．２重量部未満では、（Ａ）成分の活性化エネルギー線硬化性樹脂の光硬化反応が進行し難くなり、５０重量部を超えるとその加える量の割には効果は向上せず、むしろ経済的には不利となったり、硬化塗膜の機械的特性が低下したりすることがある。光硬化性、経済性、硬化塗膜の機械的特性などの点からは、その使用量は、好ましくは２．０〜３０重量部である。
In the present invention, the (B) photopolymerization initiator is not particularly limited, and any conventionally known photopolymerization initiator can be used. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, and 2,2-dimethoxy-2. -Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholino-propan-1-one, 4-
(2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-
Tertiary butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4 diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, P-dimethylamino Examples include benzoic acid ethyl ester. These can be used alone or in combination. The usage-amount of a photoinitiator is 0.2-50 weight part normally with respect to 100 weight part of activation energy ray-curable resins of the said (A) component. If it is less than 0.2 parts by weight, the photocuring reaction of the activated energy ray curable resin of the component (A) is difficult to proceed, and if it exceeds 50 parts by weight, the effect is not improved for the amount of addition, rather It may be disadvantageous economically or the mechanical properties of the cured coating film may be deteriorated. From the viewpoints of photocurability, economy, mechanical properties of the cured coating film, the amount used is preferably 2.0 to 30 parts by weight.
本発明における（Ｃ）希釈剤は、光重合性モノマー及び有機溶剤の少なくとも１種を意味する。光重合性モノマーは反応性希釈剤といわれるもので、これは上記（Ａ）成分の感光性樹脂の光硬化を更に十分にして、耐酸性、耐熱性、耐アルカリ性などを有する塗膜を得るために使用するもので、１分子中に二重結合を少なくとも２個有する化合物が好ましく用いられる。上記（Ａ）成分の活性化エネルギー線硬化性樹脂（感光性樹脂）を含有する感光性樹脂組成物の粘度や乾燥性を調節するために有機溶剤を用いても良いが、その必要がなければ用いなくて良い。また（Ａ）成分の感光性樹脂のみの光硬化性で足りる場合には光重合性モノマーは用いなくても良い。 The diluent (C) in the present invention means at least one of a photopolymerizable monomer and an organic solvent. The photopolymerizable monomer is referred to as a reactive diluent, and this further enhances the photocuring of the photosensitive resin as the component (A) to obtain a coating film having acid resistance, heat resistance, alkali resistance, and the like. A compound having at least two double bonds in one molecule is preferably used. An organic solvent may be used to adjust the viscosity and drying property of the photosensitive resin composition containing the activated energy ray-curable resin (photosensitive resin) as the component (A). You do not have to use it. In addition, when the photocurability of only the photosensitive resin of the component (A) is sufficient, the photopolymerizable monomer may not be used.
その光重合性モノマーの代表的なものとしては、例えば、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールアジペートジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジ（メタ）アクリレート、ジシクロペンタニルジ（メタ）アクリレート、カプロラクトン変性ジシクロペンテニルジ（メタ）アクリレート、エチレンオキサイド変性燐酸ジ（メタ）アクリレート、アリル化シクロヘキシルジ（メタ）アクリレート、イソシアヌレートジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、プロピオン酸変性ジペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、プロピレンオキシド変性トリメチロールプロパントリ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、プロピオン酸変性ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等の反応性希釈剤が挙げられる。 Typical examples of the photopolymerizable monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol. Di (meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene Oxide-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol Tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified Examples include reactive diluents such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.
上記の２〜６官能その他の多官能反応性希釈剤は単品又は複数の混合系のいずれにおいても使用可能である。この反応性希釈剤の添加量は、（Ａ）成分の活性化エネルギー線硬化性樹脂１００重量部に対して、通常２．０〜４０重量部である。その添加量が２．０重量部より少ないと十分な光硬化が得られず、硬化塗膜の耐酸性、耐熱性等において十分な特性が得られず、また、添加量が４０重量部を越えるとタックが激しく、露光の際アートワークフィルムの基板への付着が生じ易くなり、目的とする硬化塗膜が得られ難くなる。光硬化性、硬化塗膜の耐酸性、耐熱性等、アートワークフィルムの基板への付着の防止の点からは、反応性希釈剤の添加量は、好ましくは４．０〜２０重量部である。
上記の有機溶剤としては、例えばメチルエチルケトン、シクロヘキサノン等のケトン類、トルエン、キシレン等の芳香族炭化水素類、メタノール、イソプロパノール、シクロヘキサノール、などのアルコール類、シクロヘキサン、メチルシクロヘキサン等の脂環式炭化水素類、石油エーテル、石油ナフサ等の石油系溶剤類、セロソルブ、ブチルセロソルブ等のセロソルブ類、カルビトール、ブチルカルビトール等のカルビトール類、酢酸エチル、酢酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート等の酢酸エステル類等を挙げることができる。
The above-mentioned 2-6 functional and other polyfunctional reactive diluents can be used in either a single product or a plurality of mixed systems. The amount of the reactive diluent added is usually 2.0 to 40 parts by weight with respect to 100 parts by weight of the activated energy ray-curable resin as the component (A). If the addition amount is less than 2.0 parts by weight, sufficient photocuring cannot be obtained, and sufficient characteristics such as acid resistance and heat resistance of the cured coating film cannot be obtained, and the addition amount exceeds 40 parts by weight. The tackiness is severe and the artwork film tends to adhere to the substrate during exposure, making it difficult to obtain the desired cured coating film. From the viewpoint of prevention of adhesion of the artwork film to the substrate, such as photocurability, acid resistance of the cured coating film, and heat resistance, the amount of the reactive diluent is preferably 4.0 to 20 parts by weight. .
Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, isopropanol and cyclohexanol, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Petroleum solvents such as petroleum ether, petroleum naphtha, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Examples thereof include acetates such as butyl carbitol acetate.
本発明における（Ｄ）熱硬化性化合物は、上記（１）式で示される高軟化点のエポキシ樹脂を含む。
熱硬化性エポキシ化合物を含有する市販のエポキシ樹脂（ジャパンエポキシレジン株式会社製「エピコート１０３１Ｓ」等）は、フェノール樹脂やエポキシ樹脂の製造工程において、単量体と２量体以上の混合物は分子量分布が広く、また不純物も含まれるため、軟化点が低く、ソルダーレジスト組成物の熱硬化成分に用いると、熱管理幅が狭いといった問題が生じる。また、塗膜露光の際に、樹脂または不純物に起因する着色などにより、活性エネルギー線に対する透過性が低くなり、感度の低下を招くなど組成物の設計が困難であった。また、このようなエポキシ樹脂を用いると、塗膜露光及び現像後のポストキュアー後においても十分な耐熱性は得られなかった。
The (D) thermosetting compound in this invention contains the epoxy resin of the high softening point shown by the said (1) Formula.
A commercially available epoxy resin containing a thermosetting epoxy compound (such as “Epicoat 1031S” manufactured by Japan Epoxy Resin Co., Ltd.) has a molecular weight distribution of a mixture of monomers and dimers in a phenol resin or epoxy resin production process. In addition, since it contains a wide range of impurities and has a low softening point, when it is used as a thermosetting component of a solder resist composition, there is a problem that the thermal management width is narrow. In addition, it is difficult to design a composition because, for example, coloring due to a resin or impurities causes a decrease in permeability to active energy rays and a reduction in sensitivity during coating film exposure. Moreover, when such an epoxy resin was used, sufficient heat resistance was not obtained even after coating film exposure and post-curing after development.
このようなことから、上記課題を解決するため鋭意研究を行った結果、上記（１）式で示されるエポキシ化合物類において比較的低分子体で高純度のエポキシ樹脂が高軟化点を与え、このようなエポキシ樹脂を熱硬化成分としてソルダーレジスト組成物に使用すると、塗膜露光及び現像後のポストキュアー後においても十分な耐熱性、強靭な塗膜等の塗膜性能を向上させることが確認できた。 For this reason, as a result of intensive studies to solve the above problems, a relatively low molecular weight and high purity epoxy resin gives a high softening point in the epoxy compounds represented by the above formula (1). Using such an epoxy resin as a thermosetting component in a solder resist composition can be confirmed to improve coating performance such as sufficient heat resistance and tough coating even after coating exposure and post-curing after development. It was.
本発明で用いられる熱硬化性化合物として、上記（１）式で示されるエポキシ樹脂の軟化点は、１００℃以上であることが好ましく、１２０℃以上であることが更に好ましく，１４０℃以上であることが最も好ましい。またこの軟化点の上限は特にないが、２５０℃以下であることが好ましく、２００℃以下であることが更に好ましい。
また、式（１）のエポキシ樹脂が、式（２）の構造式を有するものを含むことが特に好ましい。
式（１）、式（２）において、特に好ましくは、ｎが０または１であり、Ｒ１、Ｒ２がＨ、アルキル基、フェニル基である。更に好ましくは、ｎが０であり、Ｒ１、Ｒ２がＨまたはメチル基である。
また、特に、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−メチル−４−ヒドロキシフェニル）エタンおよび１，１，２，２−テトラキス（３，５−ジメチル−４−ヒドロキシフェニル）エタンから製造されるエポキシ樹脂が好ましい。
As the thermosetting compound used in the present invention, the softening point of the epoxy resin represented by the above formula (1) is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and 140 ° C. or higher. Most preferred. The upper limit of the softening point is not particularly limited, but is preferably 250 ° C. or lower, and more preferably 200 ° C. or lower.
Moreover, it is especially preferable that the epoxy resin of Formula (1) contains what has the structural formula of Formula (2).
In formula (1) and formula (2), n is particularly preferably 0 or 1, and R 1 and R 2 are H, an alkyl group, and a phenyl group. More preferably, n is 0, and R 1 and R 2 are H or a methyl group.
In particular, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane and 1,1,2,2- Epoxy resins made from tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane are preferred.
（１）式で示される高軟化点エポキシ樹脂は、高純度（約９０％以上）の単量体を含有する市販のフェノール樹脂や、公知の方法でグリオキサール等の対応するジアルデヒドとフェノールを酸性条件下で縮合することにより調製されたフェノール樹脂またはその精製品を得て、引き続き、水酸化ナトリウム等のアルカリ存在下、過剰のエピクロルヒドリンと反応させる周知の方法により製造できる。また、当該フェノール樹脂の溶解性が極めて低い場合は、（M.Tomoi, H.Oda, H.Kakiuchi, Makromol.Chem.Rapid
Commun, 7, 143, 1986）等に記載されるような相間移動触媒を利用した方法で製造することができる。
The high softening point epoxy resin represented by the formula (1) is a commercially available phenolic resin containing a monomer of high purity (about 90% or more), or a corresponding dialdehyde such as glyoxal and phenol by a known method. A phenol resin prepared by condensing under conditions or a purified product thereof can be obtained, and subsequently produced by a well-known method of reacting with an excess of epichlorohydrin in the presence of an alkali such as sodium hydroxide. Further, when the solubility of the phenol resin is extremely low, (M. Tomoi, H. Oda, H. Kakiuchi, Makromol. Chem. Rapid.
Commun, 7, 143, 1986) and the like.
また、（Ｄ）熱硬化性成分として、（１）式で示される化合物が主成分である高軟化点のエポキシ樹脂と、（Ｄ’）他の熱硬化性エポキシ化合物を併用しても良い。（Ｄ）（１）式で示される高軟化点エポキシ樹脂の使用量は、（Ａ）紫外線硬化性樹脂１００重量部に対し、５〜５０重量部が好ましく、１０〜４５重量部が更に好ましく、１５〜３０重量部が最も好ましい。また、（Ｄ’）他の熱硬化性エポキシ樹脂を併用する場合には、（Ｄ’）の使用量は、（Ａ）紫外線硬化性樹脂１００重量部に対し、５０重量部以下が好ましく、３０重量部が更に好ましく、２０重量部以下が最も好ましい。（Ｄ’）他のエポキシ樹脂の添加により、密着性や耐めっき性改善の効果があり、一方で、使用量が多いと管理幅が狭くなり、また耐熱性の向上を阻害する。 In addition, as the thermosetting component (D), an epoxy resin having a high softening point, the main component of which is the compound represented by the formula (1), and (D ′) another thermosetting epoxy compound may be used in combination. (D) The use amount of the high softening point epoxy resin represented by the formula (1) is preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight, based on 100 parts by weight of the (A) ultraviolet curable resin. Most preferred is 15 to 30 parts by weight. In addition, when (D ′) another thermosetting epoxy resin is used in combination, the amount of (D ′) used is preferably 50 parts by weight or less with respect to 100 parts by weight of (A) ultraviolet curable resin. Part by weight is more preferable, and 20 parts by weight or less is most preferable. (D ') Addition of another epoxy resin has an effect of improving adhesion and plating resistance. On the other hand, if the amount used is large, the management range is narrowed and the improvement of heat resistance is hindered.
（Ｄ’）他の熱硬化性エポキシ化合物としては、例えばビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂環式エポキシ樹脂、（プロピレン、ポリプロピレン）グリコールジグリシジルエーテル、ポリテトラメチレングリコールジグリシジルエーテル、グリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、レゾルシンジグリシジルエーテル、１．６ヘキサンジオールジグリシジルエーテル、（エチレン、プロピレン）グリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、ソルビタンポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、トリス（２、３−エポキシプロピル）イソシアヌレート、トリグリシジルトリス（２−ヒドロキシエチル）イソシアヌレート等があげられ、また、これらエポキシ樹脂や（１）式で示される化合物が主成分であるエポキシ樹脂の一部をラジカル重合性不飽和者カルボン酸により反応させたエポキシ化合物の部分エステル化物であってもよく、そのラジカル重合性不飽和モノカルボン酸との反応において、エポキシ樹脂が有するエポキシ基の１当量当たりラジカル重合性不飽和者カルボン酸を０．１〜０．７当量反応させることが好ましく、０．３〜０．６当量反応させることが更に好ましい。これらの熱硬化性化合物は単独で用いてもよいし、複数併用してもよい。本発明における熱硬化性成分の特徴は、本発明の感光性樹脂組成物において、その塗膜を露光し、現像した後のポストキュアー後において十分な耐熱性、強靭な塗膜等の塗膜性能を向上できる点である。本発明において上記（Ａ）紫外線硬化性樹脂、（Ｂ）光重合開始剤、（Ｃ）希釈剤及び（Ｄ）熱硬化性樹脂を混合して使用することにより、本発明の感光性樹脂組成物とすることができ、例えば、プリント配線板製造用ソルダーレジスト組成物として好適に使用することができる。 (D ′) Other thermosetting epoxy compounds include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and alicyclic epoxy resins. , (Propylene, polypropylene) glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, 1.6 hexanediol diglycidyl ether, (ethylene, propylene) Glycol diglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl Ethers, tris (2,3-epoxypropyl) isocyanurate, triglycidyltris (2-hydroxyethyl) isocyanurate, and the like, and epoxy compounds mainly composed of these epoxy resins and compounds represented by the formula (1) It may be a partially esterified product of an epoxy compound obtained by reacting a part of the resin with a radical polymerizable unsaturated carboxylic acid, and in the reaction with the radical polymerizable unsaturated monocarboxylic acid, the epoxy group of the epoxy resin has It is preferable to react 0.1 to 0.7 equivalent of radically polymerizable unsaturated carboxylic acid per equivalent, and it is more preferable to react 0.3 to 0.6 equivalent. These thermosetting compounds may be used alone or in combination. The characteristic of the thermosetting component in the present invention is that the photosensitive resin composition of the present invention has sufficient heat resistance after post-curing after exposure and development of the coating film, and coating film performance such as a tough coating film. It is a point which can improve. In the present invention, the photosensitive resin composition of the present invention is used by mixing and using the above (A) ultraviolet curable resin, (B) photopolymerization initiator, (C) diluent and (D) thermosetting resin. For example, it can be suitably used as a solder resist composition for producing a printed wiring board.
（Ｄ）熱硬化性成分は、更に反応促進剤としてメラミン化合物、イミダゾール化合物、フェノール化合物等の公知のエポキシ硬化促進剤を併用して、塗膜をポストキュアーすることを促進することもできる。ジシアンジアミド、その誘導体（Ｎ−置換ジシアンジアミド誘導体（特開平１１−１１９４２９号公報に記載の一般式及び具体的例示のもの））及びこれらの有機酸塩（多塩基カルボン酸、りん酸、硫酸等の有機酸塩）の少なくとも１種を用いてもよい。この硬化促進剤の併用により、得られるレジスト皮膜の耐熱性、耐酸性、耐溶剤性、密着性、硬度などの諸特性を向上させることができ、プリント配線板用のソルダーレジストとして有用である。 (D) The thermosetting component can further promote post-curing of the coating film by using a known epoxy curing accelerator such as a melamine compound, an imidazole compound or a phenol compound as a reaction accelerator. Dicyandiamide, derivatives thereof (N-substituted dicyandiamide derivatives (general formulas and specific examples described in JP-A-11-119429)) and organic acid salts thereof (polybasic carboxylic acids, phosphoric acids, sulfuric acids, etc.) At least one kind of acid salt) may be used. The combined use of this curing accelerator can improve various properties such as heat resistance, acid resistance, solvent resistance, adhesion, and hardness of the resulting resist film, and is useful as a solder resist for printed wiring boards.
本発明の感光性樹脂組成物には、上記の成分のほかに、必要に応じて種々の添加剤、例えばシリカ、アルミナ、タルク、炭酸カルシウム、硫酸バリウム等の無機顔料からなる充填剤、フタロシアニングリーン、フタロシアニンブルー等のフタロシアニン系、アゾ系等の有機顔料や二酸化チタン等の無機顔料の公知の着色顔料、消泡剤、レベリング剤等の塗料用添加剤などを含有させることができる。 In addition to the above components, the photosensitive resin composition of the present invention includes various additives as necessary, for example, fillers composed of inorganic pigments such as silica, alumina, talc, calcium carbonate, barium sulfate, phthalocyanine green Furthermore, phthalocyanine-based organic pigments such as phthalocyanine blue, azo-based organic pigments, and known color pigments such as inorganic pigments such as titanium dioxide, paint additives such as antifoaming agents and leveling agents can be included.
上述のようにして得られた本発明の感光性樹脂組成物は、例えば銅張り積層板の銅箔をエッチングして形成した回路のパターンを有するプリント配線板に所望の厚さで塗布し、６０〜８０℃程度の温度で１５〜６０分間程度加熱して溶剤を揮散させた後、これに上記回路のパターンのはんだ付けランド以外は透光性にしたパターンのネガフィルムを密着させ、その上から紫外線を照射させ、このはんだ付けランドに対応する非露光領域を希アルカリ水溶液で除去することにより塗膜が現像される。この際使用される希アルカリ水溶液としては０．５〜５％の炭酸ナトリウム水溶液が一般的であるが、他のアルカリも使用可能である。次いで、熱硬化性化合物を含有する場合には、１３０〜１７０℃の熱風循環式の乾燥機等で２０〜８０分間ポストキュアーを行うことにより、目的とするソルダーレジスト皮膜を形成せしめることができる。このようにしてソルダーレジスト膜で被覆したプリント配線板が得られ、これに電子部品が噴流はんだ付け方法や、リフローはんだ付け方法によりはんだ付けされることにより接続、固定されて搭載され、一つの電子回路ユニットが形成される。本発明においては、その電子部品搭載前のソルダーレジスト皮膜を被覆したプリント配線板、このプリント配線板に電子部品を搭載した後のプリント配線板のいずれをもその対象に含む。なお、上記混合して使用する各成分の具体例、混合量、使用方法等は特願平１１−６７９５３号に記載されているものを適用できる。 The photosensitive resin composition of the present invention obtained as described above is applied, for example, to a printed wiring board having a circuit pattern formed by etching a copper foil of a copper-clad laminate at a desired thickness. After heating for about 15 to 60 minutes at a temperature of about ~ 80 ° C to volatilize the solvent, a negative film with a light-transmitting pattern other than the soldering land of the circuit pattern is adhered to this, and from above The coating film is developed by irradiating with ultraviolet rays and removing a non-exposed area corresponding to the soldering land with a dilute alkaline aqueous solution. The dilute alkaline aqueous solution used at this time is generally 0.5 to 5% sodium carbonate aqueous solution, but other alkalis can also be used. Subsequently, when it contains a thermosetting compound, the target soldering resist membrane | film | coat can be formed by performing a postcure for 20 to 80 minutes with a 130-170 degreeC hot-air circulation type dryer. In this way, a printed wiring board coated with a solder resist film is obtained, on which electronic components are connected, fixed and mounted by soldering by a jet soldering method or a reflow soldering method. A circuit unit is formed. In the present invention, the printed wiring board covered with the solder resist film before mounting the electronic component and the printed wiring board after mounting the electronic component on the printed wiring board are included in the object. In addition, what is described in Japanese Patent Application No. 11-67953 can be applied to the specific examples, the mixing amount, the usage method, and the like of each component used by mixing.
本発明の組成物から溶剤を除去し、ポリエチレンやポリエステル等のフィルムによりサンドイッチすることによって、感光性ドライフィルムを作製することができる。ここでいうドライフィルムは、平滑性が高く，溶剤を含まないため環境に優しく，ゴミがつかず，約60μｍの薄板にソルダーレジストの塗工が可能であり、さらに両面同時処理できるため設備が半減でき、生産効率が高いといった利点がある。 A photosensitive dry film can be produced by removing the solvent from the composition of the present invention and sandwiching it with a film of polyethylene or polyester. The dry film here has high smoothness and does not contain solvent, so it is environmentally friendly, dust-free, and can be coated with solder resist on a thin plate of about 60 μm. And has the advantage of high production efficiency.
後述する実施例で使用する各成分及びその成分比を中心に、各成分の上述した化合物の中から選択された類似化合物、各成分比の上述した好ましい範囲について、後述する実施例を包括する上位概念の発明を構成することができる。 Focusing on each component used in the examples described later and its component ratio, similar compounds selected from the above-mentioned compounds of each component, and the preferred range described above for each component ratio, the upper level including the examples described later A concept invention can be constructed.
次に、本発明を実施例によりさらに詳細に説明するが、本発明は、これらの実施例によってなんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
（エポキシアクリレート酸付加物溶液の合成）（（Ａ）成分の樹脂Ａ合成）
攪拌機、温度計、環流冷却管、滴下ロート及び窒素導入管を備えた２リットルのセパラブルフラスコにクレゾールノボラック型エポキシ樹脂（日本化薬株式会社製、ＥＣＯＮ−１０４Ｓ、軟化点９２℃、エポキシ当量２２０）６６０ｇ、カルビトールアセテート ４２１．３ｇ及びソルベントナフサ １８０．６ｇを導入し、９０℃に加熱・攪拌し、溶解した。次に一旦６０℃まで冷却し、アクリル酸 ２１６ｇ、トリフェニルホスフィン ４．０ｇ、メチルハイドロキノン １．３ｇを加えて、１００℃で１２時間反応させ、酸価が０．２ｍｇＫＯＨ／ｇの反応生成物を得た。これにテトラヒドロ無水フタル酸 ２４１．７ｇを仕込み、９０℃に加熱し、６時間反応させ、固形分酸価が８０２ｍｇＫＯＨ／ｇ、固形分濃度が６５％の樹脂溶液（樹脂Ａ）を得た。
(Synthesis of epoxy acrylate adduct solution) (Synthesis of resin A as component (A))
A 2 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introducing tube was added to a cresol novolac type epoxy resin (Nippon Kayaku Co., Ltd., ECON-104S, softening point 92 ° C., epoxy equivalent 220). ) 660 g, carbitol acetate 421.3 g and solvent naphtha 180.6 g were introduced, heated to 90 ° C. and stirred to dissolve. Next, it is once cooled to 60 ° C., 216 g of acrylic acid, 4.0 g of triphenylphosphine and 1.3 g of methylhydroquinone are added and reacted at 100 ° C. for 12 hours, and a reaction product having an acid value of 0.2 mgKOH / g is obtained. Obtained. This was charged with 241.7 g of tetrahydrophthalic anhydride, heated to 90 ° C. and reacted for 6 hours to obtain a resin solution (resin A) having a solid content acid value of 802 mg KOH / g and a solid content concentration of 65%.
（製造例１： １，１，２，２−テトラキス（４−ヒドロキシフェニル）エタンのグリシジルエーテル化合物の合成（（Ｄ）成分の熱硬化樹脂１））
攪拌機、温度計と滴下ロートを備えた５Ｌセパラブルフラスコにグリオキサール４０％水溶液１５０ｇ、フェノール３００ｇと２Ｌのメタノールを加えた溶液を氷浴で０〜５℃に冷却し、溶液の温度を１０℃以下に保ちながら撹拌しながら濃硫酸（９８％）１Ｌを５時間かけて滴下した。滴下後、更に２時間反応させ、反応溶液を５Ｌの水で希釈した。生じた固体は熱水とアセトンで洗い、乾燥した（収量１９５ｇ）。このフェノール樹脂の純度はＨＰＬＣで９３％であった。
引き続いて、得られたフェノール樹脂５０ｇ、エピクロルヒドリン４００ｇとテトラブチルアンモニウムブロミド２ｇを窒素雰囲気下、１００℃、３時間加熱した後、室温まで冷却した。その後２５℃で４０％水酸化ナトリウム水溶液２０ｇを３時間かけて滴下し、更に２５℃で１２時間撹拌させ、その後未反応のエピクロルヒドリンを減圧除去した。残渣をメチルイソブチルケトンで抽出、温水洗浄し、溶剤を減圧除去した。淡黄色固体をアセトンとイソプロパノールから再結晶し白色固体を得た（収量５５ｇ）。
軟化点１６５℃。 エポキシ当量１７９ｇ／ｅｇ。 構造解析は１Ｈ-ＮＭＲにより行い、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタンのグリシジルエーテル化合物と確認された。ゲルパーミエーションクロマトグラフィーによるテトラキスフェノール化合物の含有率（面積比）は８５％であった。
(Production Example 1: Synthesis of glycidyl ether compound of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane (thermosetting resin 1 of component (D)))
A solution obtained by adding 150 g of 40% aqueous solution of glyoxal, 300 g of phenol and 2 L of methanol to a 5 L separable flask equipped with a stirrer, a thermometer and a dropping funnel is cooled to 0 to 5 ° C. in an ice bath, and the temperature of the solution is 10 ° C. or less. 1 L of concentrated sulfuric acid (98%) was added dropwise over 5 hours while stirring. After the dropwise addition, the reaction was further continued for 2 hours, and the reaction solution was diluted with 5 L of water. The resulting solid was washed with hot water and acetone and dried (yield 195 g). The purity of this phenol resin was 93% by HPLC.
Subsequently, 50 g of the obtained phenol resin, 400 g of epichlorohydrin and 2 g of tetrabutylammonium bromide were heated at 100 ° C. for 3 hours in a nitrogen atmosphere, and then cooled to room temperature. Thereafter, 20 g of a 40% aqueous sodium hydroxide solution was added dropwise at 25 ° C. over 3 hours, and the mixture was further stirred at 25 ° C. for 12 hours. Thereafter, unreacted epichlorohydrin was removed under reduced pressure. The residue was extracted with methyl isobutyl ketone, washed with warm water, and the solvent was removed under reduced pressure. The pale yellow solid was recrystallized from acetone and isopropanol to obtain a white solid (yield 55 g).
Softening point 165 ° C. Epoxy equivalent 179 g / eg. Structural analysis was performed by 1 H-NMR, and it was confirmed to be a glycidyl ether compound of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane. The content (area ratio) of the tetrakisphenol compound by gel permeation chromatography was 85%.
（製造例２： １，１，２，２−テトラキス（３−メチル−４−ヒドロキシフェニル）エタンのグリシジルエーテル化合物の合成（（Ｄ）成分の熱硬化樹脂２））
攪拌機、温度計、環流冷却管、滴下ロート及び窒素導入管を備えた２００ｍＬフラスコに１，１，２，２−テトラキス（３−メチル−４−ヒドロキシフェニル）エタン（本州化学工業株式会社製）１０ｇ、エピクロルヒドリン１００ｇとテトラブチルアンモニウムブロミド０．５ｇを窒素雰囲気下、１００℃、３時間加熱した後、室温まで冷却した。その後２５℃で４０％水酸化ナトリウム水溶液４ｇを３時間かけて滴下し、更に２５℃で１２時間撹拌させ、その後未反応のエピクロルヒドリンを減圧除去した。残渣をメチルイソブチルケトンで抽出、温水洗浄し、溶剤を減圧除去した。淡黄色固体をアセトンとイソプロパノールから再結晶し白色固体を得た（収量１１ｇ）。
軟化点１２８℃。 エポキシ当量１９３。 構造解析は１Ｈ-ＮＭＲにより行い、１，１，２，２−テトラキス（３−メチル−４−ヒドロキシフェニル）エタンのグリシジルエーテル化合物と確認された。ゲルパーミエーションクロマトグラフィーによるテトラキスフェノール化合物の含有率（面積比）は８２％であった。
(Production Example 2: Synthesis of glycidyl ether compound of 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane (thermosetting resin 2 of component (D)))
10 g of 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane (manufactured by Honshu Chemical Industry Co., Ltd.) in a 200 mL flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube Then, 100 g of epichlorohydrin and 0.5 g of tetrabutylammonium bromide were heated in a nitrogen atmosphere at 100 ° C. for 3 hours, and then cooled to room temperature. Thereafter, 4 g of 40% aqueous sodium hydroxide solution was added dropwise at 25 ° C. over 3 hours, and the mixture was further stirred at 25 ° C. for 12 hours. Thereafter, unreacted epichlorohydrin was removed under reduced pressure. The residue was extracted with methyl isobutyl ketone, washed with warm water, and the solvent was removed under reduced pressure. The pale yellow solid was recrystallized from acetone and isopropanol to obtain a white solid (yield 11 g).
Softening point 128 ° C. Epoxy equivalent 193. Structural analysis was performed by 1 H-NMR, and it was confirmed to be a glycidyl ether compound of 1,1,2,2-tetrakis (3-methyl-4-hydroxyphenyl) ethane. The content (area ratio) of the tetrakisphenol compound by gel permeation chromatography was 82%.
（製造例３： １，１，２，２−テトラキス（３，５−ジメチル−４−ヒドロキシフェニル）エタンのグリシジルエーテル化合物の合成（（Ｄ）成分の熱硬化樹脂３））
１，１，２，２−テトラキス（３．５−ジメチル−４−ヒドロキシフェニル）エタン（本州化学工業株式会社製）１０ｇを使用した以外は製造例２と同様に行った（収量１０ｇ）。
軟化点１１３℃。 エポキシ当量１９９。 構造解析は１Ｈ-ＮＭＲにより行い、１，１，２，２−テトラキス（３，５−ジメチル−４−ヒドロキシフェニル）エタンのグリシジルエーテル化合物と確認された。ゲルパーミエーションクロマトグラフィーによるテトラキスフェノール化合物の含有率（面積比）は８３％であった。
(Production Example 3: Synthesis of glycidyl ether compound of 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane ((D) component thermosetting resin 3))
The procedure was the same as in Production Example 2 except that 10 g of 1,1,2,2-tetrakis (3.5-dimethyl-4-hydroxyphenyl) ethane (Honshu Chemical Industry Co., Ltd.) was used (yield 10 g).
Softening point 113 ° C. Epoxy equivalent 199. Structural analysis was performed by 1 H-NMR, and it was confirmed to be a glycidyl ether compound of 1,1,2,2-tetrakis (3,5-dimethyl-4-hydroxyphenyl) ethane. The content (area ratio) of the tetrakisphenol compound by gel permeation chromatography was 83%.
（実施例１（感光性樹脂組成物の製造））
上記で合成したエポキシアクリレート酸付加物溶液（樹脂Ａ）１００ ｇに対し、２−メチル−１−［４−(メチルチオ)フェニル］−２ ‐モルフォリノ−１‐プロパノン（チバ・スペシャリティ・ケミカルズ株式会社製、イルガキュア９０７）を８．０ ｇ、ペンタエリスリトールを８．０
ｇ、フタロシアニングリーンを０．５ ｇ及びタルクを８．０ ｇと上記製造例１で合成した熱硬化樹脂１を２０ｇの割合で配合し、これらを３本ロールで混合分散させて、感光性樹脂組成物の溶液を調製した。この感光性樹脂組成物の塗膜の感度、熱管理幅及び塗膜性能を後述の試験法によって調べた結果を表１に示す。
(Example 1 (Production of photosensitive resin composition))
2-Methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone (Ciba Specialty Chemicals Co., Ltd.) was added to 100 g of the epoxy acrylate acid adduct solution (resin A) synthesized above. , Irgacure 907) 8.0 g, pentaerythritol 8.0 g
g, 0.5 g of phthalocyanine green and 8.0 g of talc and 20 g of the thermosetting resin 1 synthesized in the above Production Example 1, and mixing and dispersing them with three rolls to obtain a photosensitive resin A solution of the composition was prepared. Table 1 shows the results of examining the sensitivity of the coating film, the thermal management width and the coating film performance of this photosensitive resin composition by the test method described later.
（実施例２）
実施例１において、樹脂の製造例２で得られた熱硬化樹脂２を使用し、その他の組成は同様にして感光性樹脂組成物の溶液を調製した。この感光性樹脂組成物の塗膜の感度、熱管理幅及び塗膜性能を実施例１と同様にして調べた結果を表１に示す。
(Example 2)
In Example 1, the thermosetting resin 2 obtained in Resin Production Example 2 was used, and a solution of the photosensitive resin composition was prepared in the same manner for the other compositions. Table 1 shows the results of examining the sensitivity, thermal management width, and coating performance of the photosensitive resin composition in the same manner as in Example 1.
（実施例３）
実施例１において、樹脂の製造例３で得られた熱硬化樹脂３を使用し、ペンタエリスリトールを５．０ｇに添加量を変えた以外は同様にして感光性樹脂組成物の溶液を調製した。この感光性樹脂組成物の塗膜の感度、熱管理幅及び塗膜性能を実施例１と同様にして調べた結果を表１に示す。
(Example 3)
In Example 1, a solution of the photosensitive resin composition was prepared in the same manner except that the thermosetting resin 3 obtained in Resin Production Example 3 was used and the addition amount of pentaerythritol was changed to 5.0 g. Table 1 shows the results of examining the sensitivity, thermal management width, and coating performance of the photosensitive resin composition in the same manner as in Example 1.
（実施例４）
実施例１において、樹脂の製造例１で得られた熱硬化樹脂１と製造例３で得られた熱硬化樹脂３を各１０ｇ使用し、ペンタエリスリトール添加量を５．０ｇに変えた以外は同様にして感光性樹脂組成物の溶液を調製した。この感光性樹脂組成物の塗膜の感度、熱管理幅及び塗膜性能を実施例１と同様にして調べた結果を表１に示す。
Example 4
In Example 1, the thermosetting resin 1 obtained in Production Example 1 of the resin and the thermosetting resin 3 obtained in Production Example 3 were each used in an amount of 10 g, and the pentaerythritol addition amount was changed to 5.0 g. Thus, a solution of the photosensitive resin composition was prepared. Table 1 shows the results of examining the sensitivity, thermal management width, and coating performance of the photosensitive resin composition in the same manner as in Example 1.
（実施例５）
実施例１において、樹脂の製造例２で得られた熱硬化樹脂２を２０ｇ、製造例３で得られた熱硬化樹脂３を１０ｇ使用し、その他は同様にして感光性樹脂組成物の溶液を調製した。この感光性樹脂組成物の塗膜の感度、熱管理幅及び塗膜性能を実施例１と同様にして調べた結果を表１に示す。
(Example 5)
In Example 1, 20 g of the thermosetting resin 2 obtained in Production Example 2 of the resin was used, and 10 g of the thermosetting resin 3 obtained in Production Example 3 was used. Prepared. Table 1 shows the results of examining the sensitivity, thermal management width, and coating performance of the photosensitive resin composition in the same manner as in Example 1.
（実施例６）
実施例１において、樹脂の製造例３で得られた熱硬化樹脂３を１５ｇ、更にフェノールノボラック型エポキシ樹脂（ジャパンエポキシレジン株式会社製：エピコート１５２、エポキシ当量１７５ｇ／ｅｇ）を５ｇ加え、その他は同様にして感光性樹脂組成物の溶液を調製した。この感光性樹脂組成物の塗膜の感度、熱管理幅及び塗膜性能を実施例１と同様にして調べた結果を表１に示す。
(Example 6)
In Example 1, 15 g of thermosetting resin 3 obtained in Resin Production Example 3 was added, and 5 g of phenol novolac type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: Epicoat 152, epoxy equivalent 175 g / eg) was added. Similarly, a solution of the photosensitive resin composition was prepared. Table 1 shows the results of examining the sensitivity, thermal management width, and coating performance of the photosensitive resin composition in the same manner as in Example 1.
（比較例１〜３）
実施例１において、樹脂の製造例１で得られた熱硬化性樹脂の代わりに、表１で示したエポキシ樹脂各２０ｇ使用し、その他は同様にして感光性樹脂組成物の溶液を調製した。この感光性樹脂組成物の塗膜の感度、熱管理幅及び塗膜性能を実施例１と同様にして調べた結果を表１に示す。
(Comparative Examples 1-3)
In Example 1, 20 g of each epoxy resin shown in Table 1 was used instead of the thermosetting resin obtained in Resin Production Example 1, and a solution of the photosensitive resin composition was prepared in the same manner. Table 1 shows the results of examining the sensitivity, thermal management width, and coating performance of the photosensitive resin composition in the same manner as in Example 1.
感光性樹脂組成物の塗膜の感度、熱管理幅及び塗膜性能の評価方法は、以下のとおりである。
予め面処理済みの基板に、スクリーン印刷法により、上記実施例１〜６、比較例１〜３のそれぞれの感光性樹脂組成物を３５μｍの厚さ（乾燥前）に塗工してそれぞれの塗工基板を作製した。
塗膜性能の評価用試験片は、上記塗工基板にアートワークフィルムを通しメインピ−クが３６５ｎｍの波長の紫外線の照射光量をオ−ク製作所社製の積算光量計を用い３００ｍＪ／ｃｍ２
照射し、１％の炭酸ナトリウム水溶液を用い、２．０ｋｇ／ｃｍ２ のスプレ−圧で６０秒間現像を行った後、１５０℃、１時間ポストキュアして硬化塗膜を有する基板を作成した。
The evaluation method of the sensitivity of the coating film of the photosensitive resin composition, the thermal management width, and the coating film performance is as follows.
Each of the photosensitive resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3 is applied to a surface-treated substrate in a thickness of 35 μm (before drying) by screen printing. A processed substrate was prepared.
The test piece for evaluating the coating film performance is 300 mJ / cm 2 using an integrating light meter manufactured by Oak Seisakusho Co., Ltd. with the artwork film being passed through the coated substrate and the main peak being irradiated with ultraviolet light having a wavelength of 365 nm.
The substrate was irradiated and developed with a 1% aqueous sodium carbonate solution at a spray pressure of 2.0 kg / cm 2 for 60 seconds, and then post-cured at 150 ° C. for 1 hour to prepare a substrate having a cured coating film.
（感度）
上述の塗工基板を８０℃、２０分予備乾燥した後の塗工基板に感度測定用ステップタブレット（コダック２１段）を設置し、ステップタブレットを通しメインピ−クが３６５ｎｍの波長の紫外線の照射光量をオ−ク製作所社製の積算光量計を用い３００ｍＪ／ｃｍ２
照射したものをテストピ−スとし、１％の炭酸ナトリウム水溶液を用い、２．０ｋｇ／ｃｍ２ のスプレ−圧で６０秒間現像を行った後の露光部分の除去されない部分を数字（ステップ数）で表した。ステップ数が大きいほど感光特性が良好であることを示す。
(sensitivity)
A step tablet for sensitivity measurement (21 stages of Kodak) is installed on the coated substrate after the above-mentioned coated substrate is pre-dried at 80 ° C. for 20 minutes, and the amount of ultraviolet light with a main peak of 365 nm is passed through the step tablet. Is 300 mJ / cm 2 using an integrating photometer manufactured by Oak Manufacturing Co., Ltd.
The irradiated part is used as a test piece, and a 1% sodium carbonate aqueous solution is used and the exposed part after development for 60 seconds at a spray pressure of 2.0 kg / cm 2 is indicated by a number (number of steps). expressed. The larger the number of steps, the better the photosensitive characteristics.
（熱管理幅）
上述の塗工基板の予備乾燥時間を１０分間隔で１２０分まで延長したものを試験片とし、１％の炭酸ナトリウム水溶液を用い、２．０ｋｇ／ｃｍ２
のスプレー圧で６０秒現像を行い、塗工膜を完全に除去することができる最長の予備乾燥時間（ｍｉｎ）を測定した。
(Thermal management width)
Pre-drying time of the coating substrate described above was used as a test piece which was extended to 120 minutes at 10 minute intervals, using a 1% aqueous solution of sodium carbonate, 2.0 kg / cm 2
Development was carried out at a spray pressure of 60 seconds, and the longest preliminary drying time (min) at which the coated film could be completely removed was measured.
（タック性（指触乾燥性））
上述の塗工基板を８０℃、２０分予備乾燥した後、塗膜表面にネガフィルムを密着させ、露光した後に、ネガフィルムへの塗膜の付着の程度を調べ、以下のように評価した。
◎：まったく付着、貼り付き跡が認められないもの
○：塗膜表面に貼り付き跡が認められるもの
△：剥離に際し、抵抗が生じるもの
×：ネガフィルムへの塗膜の付着が認められるもの
(Tackiness (dryness to touch))
After the above-mentioned coated substrate was preliminarily dried at 80 ° C. for 20 minutes, the negative film was brought into close contact with the surface of the coating film and exposed, and then the degree of adhesion of the coating film to the negative film was examined and evaluated as follows.
◎: No sticking or sticking marks are observed. ○: Sticking marks are observed on the coating film surface. Δ: Resistance is generated upon peeling. X: Coating film is adhered to the negative film.
（鉛筆硬度）
硬化塗膜をＪＩＳ Ｃ ５０１２−１９９３ ８．６．３に準拠して測定した。
(Pencil hardness)
The cured coating film was measured according to JIS C 5012-1993 8.6.3.
（はんだ耐熱性）
硬化塗膜を有する試験片を、ＪＩＳ Ｃ ６４８１の試験方法に従って、２６０℃のはんだ槽に３０秒浸漬後、セロハンテープによるピーリング試験を１サイクルとした計１〜３サイクルを行った後の塗膜状態を目視により評価した。
◎：３サイクル後も塗膜に変化がないもの
○：３サイクル後に僅かに変化しているもの
△：２サイクル後に変化しているもの
×：１サイクル後に剥離を生じるもの
(Solder heat resistance)
After the test piece having a cured coating film was immersed in a solder bath at 260 ° C. for 30 seconds in accordance with the test method of JIS C 6481, the coating film was subjected to a total of 1 to 3 cycles with a peeling test using a cellophane tape as one cycle. The state was evaluated visually.
◎: No change in coating film after 3 cycles ○: Slight change after 3 cycles Δ: Change after 2 cycles ×: Peeling after 1 cycle
（耐溶剤性）
硬化塗膜を有する試験基板を常温の塩化メチレンに３０分間浸漬したのち、水洗後、セロハン粘着テープによるピーリング試験を行い、塗膜の剥がれ、変色について観察し、耐溶剤性を評価した。
◎：全く変化が認められないもの
○：ほんの僅か変化しているもの
△：顕著に変化しているもの
×：塗膜が膨潤して剥離したもの
(Solvent resistance)
A test substrate having a cured coating film was immersed in methylene chloride at room temperature for 30 minutes, washed with water, then subjected to a peeling test using a cellophane adhesive tape, and the coating film was observed for peeling and discoloration to evaluate solvent resistance.
◎: No change at all ○: Slightly changed Δ: Significantly changed ×: Swelled and peeled off
（耐金メッキ性）
硬化塗膜を有する試験基板に金メッキ加工後、セロハン粘着テープによるピーリング試験を行い、塗膜の剥がれ、変色について観察し、耐金メッキ性を評価した。
◎：全く変化が認められないもの
○：ほんの僅かに変化したもの
△：顕著に変化しているもの
×：塗膜が膨潤して剥離したもの
（電気特性）
電気特性は、ＩＰＣ−ＴＭ−６５０のＩＰＣ−ＳＭ８４０Ｂ Ｂ−２５テストクーポンのくし形電極を用い、８５℃、８５％、Ｒ．Ｈ．で２００時間加湿した後の絶縁抵抗を、ＤＣ５０Ｖを印加して測定した。
(Gold resistance)
A gold-plated test substrate having a cured coating film was subjected to a peeling test using a cellophane adhesive tape, and the coating film was observed for peeling and discoloration to evaluate the gold plating resistance.
◎: No change at all ◯: Slightly changed △: Significant change ×: Swelled and peeled off (electrical properties)
The electrical properties were measured using IPC-TM-650 IPC-SM840B B-25 test coupon comb electrode, 85 ° C., 85%, R.P. H. The insulation resistance after humidifying for 200 hours was measured by applying DC 50V.
＊２：ジャパンエポキシレジン株式会社製（エポキシ当量 １７５ｇ／ｅｇ）
＊３：日産化学工業株式会社製（エポキシ当量１０１ｇ／ｅｇ）
* 2: Made by Japan Epoxy Resin Co., Ltd. (epoxy equivalent 175 g / eg)
* 3: Made by Nissan Chemical Industries, Ltd. (epoxy equivalent 101 g / eg)
表１の結果から、本発明の式（１）で示される高軟化点エポキシ樹脂を熱硬化性化合物として用いた実施例１〜６は、エポキシ系熱硬化化合物のみを用いた比較例１〜３に比較し、感度、熱管理幅、タック性及びはんだ耐熱性に優れた感光性樹脂組成物を設計できることがわかる。また、本発明の高軟化点エポキシ樹脂と他のエポキシ系熱硬化化合物を組合せることにより、塗膜特性を維持しながら、耐金めっき性に優れた感光性樹脂組成物を設計できることがわかる。 From the result of Table 1, Examples 1-6 which used the high softening point epoxy resin shown by Formula (1) of this invention as a thermosetting compound are Comparative Examples 1-3 using only an epoxy-type thermosetting compound. It can be seen that a photosensitive resin composition excellent in sensitivity, thermal management width, tackiness and solder heat resistance can be designed. Moreover, it turns out that the photosensitive resin composition excellent in gold-plating resistance can be designed, maintaining a coating-film characteristic by combining the high softening point epoxy resin of this invention, and another epoxy type thermosetting compound.
本発明によれば、紫外線露光及び希アルカリ水溶液による現像で画像形成可能であり、耐熱性に優れるとともに、タック性（指触乾燥性）、熱管理幅、感度、耐熱性に優れ、そのほかの塗膜性能も良く維持する事ができる。更には、耐金めっき性等の使用目的に合わせた特性が得られるような設計を容易に行うことができる。そして、その感光性樹脂組成物のソルダーレジスト硬化膜を有する電子部品搭載前又は後のプリント配線板を提供することができる。
According to the present invention, it is possible to form an image by ultraviolet exposure and development with a dilute aqueous alkali solution, which is excellent in heat resistance, tackiness (dryness to touch), thermal management width, sensitivity, heat resistance, and other coatings. The membrane performance can be maintained well. Furthermore, it is possible to easily carry out a design so as to obtain characteristics tailored to the purpose of use such as gold plating resistance. And the printed wiring board before or after electronic component mounting which has the soldering resist cured film of the photosensitive resin composition can be provided.
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| JP2003396958A JP4274914B2 (en) | 2003-11-27 | 2003-11-27 | Solder resist composition and printed wiring board |
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| JP2003396958A JP4274914B2 (en) | 2003-11-27 | 2003-11-27 | Solder resist composition and printed wiring board |
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| JP4274914B2 JP4274914B2 (en) | 2009-06-10 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007284582A (en) * | 2006-04-18 | 2007-11-01 | Nippon Kayaku Co Ltd | Epoxy resin, epoxy resin composition, and cured product thereof |
| WO2014092019A1 (en) * | 2012-12-12 | 2014-06-19 | 株式会社ニコン | Composition, laminate, method for producing laminate, transistor, and method for producing transistor |
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2003
- 2003-11-27 JP JP2003396958A patent/JP4274914B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007284582A (en) * | 2006-04-18 | 2007-11-01 | Nippon Kayaku Co Ltd | Epoxy resin, epoxy resin composition, and cured product thereof |
| WO2014092019A1 (en) * | 2012-12-12 | 2014-06-19 | 株式会社ニコン | Composition, laminate, method for producing laminate, transistor, and method for producing transistor |
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| JP4274914B2 (en) | 2009-06-10 |
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