JP2937800B2 - Composition for solder photoresist ink - Google Patents
Composition for solder photoresist inkInfo
- Publication number
- JP2937800B2 JP2937800B2 JP9600195A JP9600195A JP2937800B2 JP 2937800 B2 JP2937800 B2 JP 2937800B2 JP 9600195 A JP9600195 A JP 9600195A JP 9600195 A JP9600195 A JP 9600195A JP 2937800 B2 JP2937800 B2 JP 2937800B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- curable resin
- photoresist ink
- anhydride
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 74
- 229910000679 solder Inorganic materials 0.000 title claims description 67
- 229920002120 photoresistant polymer Polymers 0.000 title claims description 60
- 229920005989 resin Polymers 0.000 claims description 110
- 239000011347 resin Substances 0.000 claims description 110
- 150000001875 compounds Chemical class 0.000 claims description 42
- 239000004593 Epoxy Substances 0.000 claims description 41
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 38
- 150000008065 acid anhydrides Chemical class 0.000 claims description 36
- 229920003986 novolac Polymers 0.000 claims description 36
- 239000003085 diluting agent Substances 0.000 claims description 25
- 239000007795 chemical reaction product Substances 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 21
- 229920001187 thermosetting polymer Polymers 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 238000013329 compounding Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 51
- 239000003513 alkali Substances 0.000 description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 27
- 238000004519 manufacturing process Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 25
- 150000008064 anhydrides Chemical class 0.000 description 21
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 229940014800 succinic anhydride Drugs 0.000 description 15
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- 238000003860 storage Methods 0.000 description 12
- 238000010292 electrical insulation Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- -1 alicyclic hydrocarbons Chemical class 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 230000004907 flux Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000298 Cellophane Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 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 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- PIYNUZCGMLCXKJ-UHFFFAOYSA-N 1,4-dioxane-2,6-dione Chemical compound O=C1COCC(=O)O1 PIYNUZCGMLCXKJ-UHFFFAOYSA-N 0.000 description 1
- RXYVNNWGXQRJAC-UHFFFAOYSA-N 1-chloro-1-[3-(trifluoromethyl)phenyl]propan-2-one Chemical compound CC(=O)C(Cl)C1=CC=CC(C(F)(F)F)=C1 RXYVNNWGXQRJAC-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 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 1
- SYIUWAVTBADRJG-UHFFFAOYSA-N 2H-pyran-2,6(3H)-dione Chemical compound O=C1CC=CC(=O)O1 SYIUWAVTBADRJG-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- DFATXMYLKPCSCX-UHFFFAOYSA-N 3-methylsuccinic anhydride Chemical compound CC1CC(=O)OC1=O DFATXMYLKPCSCX-UHFFFAOYSA-N 0.000 description 1
- WUMMIJWEUDHZCL-UHFFFAOYSA-N 3-prop-2-enyloxolane-2,5-dione Chemical compound C=CCC1CC(=O)OC1=O WUMMIJWEUDHZCL-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- ROFZMKDROVBLNY-UHFFFAOYSA-N 4-nitro-2-benzofuran-1,3-dione Chemical compound [O-][N+](=O)C1=CC=CC2=C1C(=O)OC2=O ROFZMKDROVBLNY-UHFFFAOYSA-N 0.000 description 1
- GOYGTBXFJBGGLI-UHFFFAOYSA-N 7a-but-1-enyl-3a-methyl-4,5-dihydro-2-benzofuran-1,3-dione Chemical compound C1=CCCC2(C)C(=O)OC(=O)C21C=CCC GOYGTBXFJBGGLI-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LYDODUOPDJULET-UHFFFAOYSA-N CC1=C(C(=C(C(=O)[PH2]=O)C=C1)C)C Chemical compound CC1=C(C(=C(C(=O)[PH2]=O)C=C1)C)C LYDODUOPDJULET-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 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 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- AOLRWAIABWHYDS-UHFFFAOYSA-N isochromene-1,3,4-trione Chemical compound C1=CC=C2C(=O)C(=O)OC(=O)C2=C1 AOLRWAIABWHYDS-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ソルダーフォトレジス
トインキ用組成物に関する。さらに詳しくは、本発明
は、プリント配線基板のソルダーマスク用のフォトレジ
スト、プリント配線基板を製造する際の銅エッチング用
フォトレジスト、光照射によってパターン形成を行うた
めの文字インク用感光性樹脂として有用であり、貯蔵安
定性が良好で、希アルカリ現像性に優れ、耐熱性、電気
絶縁性及び耐湿性に優れた硬化塗膜を与えるソルダーフ
ォトレジストインキ用組成物に関する。FIELD OF THE INVENTION The present invention relates to a composition for a solder photoresist ink. More specifically, the present invention is useful as a photoresist for a solder mask of a printed wiring board, a photoresist for copper etching when manufacturing a printed wiring board, and a photosensitive resin for character ink for performing pattern formation by light irradiation. The present invention relates to a composition for a solder photoresist ink which has a good storage stability, is excellent in dilute alkali developability, and provides a cured coating film having excellent heat resistance, electrical insulation and moisture resistance.
【０００２】[0002]
【従来の技術】現在、各種プリント配線基板のソルダー
レジストは、スクリーン印刷による熱硬化型液状レジス
ト樹脂及びドライフィルム型のレジスト樹脂から、希ア
ルカリ現像型の液状ソルダーフォトレジストインキへと
移行している。このようなソルダーフォトレジストイン
キ用組成物としては、例えば、ノボラック型エポキシ化
合物と不飽和モノカルボン酸との反応生成物に、飽和又
は不飽和多塩基酸無水物を反応させて得られる紫外線硬
化性樹脂、光重合開始剤及び希釈剤からなる第１液成分
と、１分子中に２個以上のエポキシ基を有するエポキシ
化合物である熱硬化性成分及び希釈剤からなる第２液成
分とを、使用直前に混合して用いる２液型の組成物が知
られている（特公平１−５４３９０号公報）。２液を混
合することにより得られるソルダーフォトレジストイン
キ用組成物を、プリント配線基板に塗布し、仮乾燥工程
により塗布表面をタックフリーにしたのち、フォトマス
クを用いて紫外線露光を行い、希アルカリ水溶液で現像
処理して未露光部分を除去し、さらに加熱により露光部
分を完全に熱硬化させる。しかし、これら従来の希アル
カリ現像型紫外線硬化性樹脂は、樹脂中に反応性の高い
不飽和結合及びカルボキシル基を有するため、保存中に
分子量が増加しやすく、シェルフライフが短いという欠
点がある。また、これらの樹脂を用いたソルダーフォト
レジストインキ用組成物は、レジストインキの粘度上昇
を避けるため、２液型としてエポキシ化合物を使用直前
に配合するにもかかわらず、同一液中に反応性の高い不
飽和結合、カルボキシル基及び光重合開始剤を含むた
め、フォトレジストインキの安定性が低く、ポットライ
フが短いという欠点があった。また、多塩基酸無水物や
光重合開始剤の種類や配合量の調整によって、紫外線硬
化性樹脂のシェルフライフやフォトレジストインキのポ
ットライフを向上させると、貯蔵安定性の向上と引き換
えに、希アルカリ現像性や光硬化性などのソルダーフォ
トレジストインキの製造工程における特性、及び、耐熱
性、電気絶縁性、耐湿性などのソルダーレジスト塗膜と
しての性能が低下するという欠点があった。2. Description of the Related Art At present, solder resists for various printed wiring boards are shifting from screen-printed thermosetting type liquid resist resins and dry film type resist resins to dilute alkali developing type liquid solder photoresist inks. . Examples of such a composition for a solder photoresist ink include, for example, an ultraviolet curable composition obtained by reacting a reaction product of a novolak type epoxy compound with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride. A first liquid component comprising a resin, a photopolymerization initiator, and a diluent, and a second liquid component comprising a thermosetting component, which is an epoxy compound having two or more epoxy groups in one molecule, and a diluent, are used. A two-pack type composition used immediately before mixing is known (Japanese Patent Publication No. 1-54390). The composition for solder photoresist ink obtained by mixing the two liquids is applied to a printed wiring board, and the applied surface is tack-free by a preliminary drying step, and then exposed to ultraviolet light using a photomask, and diluted with a dilute alkali. Unexposed portions are removed by developing with an aqueous solution, and the exposed portions are completely thermally cured by heating. However, these conventional dilute alkali-developable ultraviolet curable resins have highly reactive unsaturated bonds and carboxyl groups in the resin, and therefore have the disadvantage that the molecular weight tends to increase during storage and the shelf life is short. In addition, in order to avoid a rise in the viscosity of the resist ink, the composition for a solder photoresist ink using these resins is reactive in the same liquid even though the epoxy compound is blended immediately before use as a two-part type. Since it contains a high unsaturated bond, a carboxyl group, and a photopolymerization initiator, it has the disadvantage that the stability of the photoresist ink is low and the pot life is short. In addition, if the shelf life of the ultraviolet curable resin and the pot life of the photoresist ink are improved by adjusting the types and the amounts of the polybasic acid anhydride and the photopolymerization initiator, the storage stability is improved. There are drawbacks in that properties in the manufacturing process of the solder photoresist ink such as alkali developability and photocurability, and performance as a solder resist coating film such as heat resistance, electrical insulation and moisture resistance are reduced.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、従来の紫外
線硬化性樹脂及びそれを含む希アルカリ現像型ソルダー
フォトレジストインキにおける貯蔵安定性の向上を目指
し、具体的には、紫外線硬化性樹脂の形態で長期間粘度
の増加がなく、紫外線硬化性樹脂に光重合開始剤、希釈
剤を配合し、ソルダーフォトレジストインキ用組成物と
して長期間粘度の増加がなく、しかも光硬化性、希アル
カリ現像性、耐熱性、耐湿性、電気絶縁特性が優れたソ
ルダーフォトレジストインキ用組成物を提供することを
目的としてなされたものである。SUMMARY OF THE INVENTION The present invention aims at improving the storage stability of a conventional ultraviolet curable resin and a dilute alkali developing type solder photoresist ink containing the same. No increase in viscosity for a long time in the form, blended photopolymerization initiator and diluent with UV curable resin, no increase in viscosity for long term as a composition for solder photoresist ink, and photocurable, diluted alkali development An object of the present invention is to provide a composition for a solder photoresist ink having excellent heat resistance, heat resistance, moisture resistance, and electrical insulation properties.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく鋭意研究を重ねた結果、ノボラック型エ
ポキシ化合物と不飽和モノカルボン酸との反応生成物
に、２種以上の二塩基酸を同時に反応して得られる紫外
線硬化性樹脂を含有する組成物が、貯蔵安定性と希アル
カリ現像性に優れ、しかもその硬化物が良好な機械的、
化学的特性を有することを見いだし、この知見に基づい
て本発明を完成するに至った。すなわち、本発明は、
（１）紫外線硬化性樹脂、光重合開始剤、希釈剤及び熱
硬化性樹脂を含有するソルダーフォトレジストインキ用
組成物において、紫外線硬化性樹脂が、ノボラック型エ
ポキシ化合物と不飽和モノカルボン酸との反応生成物
に、分子量が１２０以下の二塩基酸無水物及び分子量が
１４０以上の二塩基酸無水物をモル比が１／９〜９／１
となる割合で、同時に反応することにより得られるもの
であることを特徴とするソルダーフォトレジストインキ
用組成物、（２）ノボラック型エポキシ化合物のフェノ
ール核の核数が、平均４核以上８核以下である第(１)項
記載のソルダーフォトレジストインキ用組成物、（３）
ノボラック型エポキシ化合物のエポキシ基に対し、当量
の不飽和モノカルボン酸を反応させるものである第(１)
〜(２)項記載のソルダーフォトレジストインキ用組成
物、（４）紫外線硬化性樹脂が、ノボラック型エポキシ
化合物と不飽和モノカルボン酸との反応生成物の有する
水酸基１モル当たり、０.３〜１.０モルの二塩基酸無水
物を反応させたものである第(１)〜(３)項記載のソルダ
ーフォトレジストインキ用組成物、（５）紫外線硬化性
樹脂が、４０〜１００mgKOH／ｇの酸価を有するもので
ある第(１)〜(４)項記載のソルダーフォトレジストイン
キ用組成物、（６）光重合開始剤の配合量が、紫外線硬
化性樹脂１００重量部当たり０.２〜２０.０重量部であ
る第(１)〜(５)項記載のソルダーフォトレジストインキ
用組成物、（７）希釈剤が、有機溶剤及び光重合性モノ
マーの中から選ばれた少なくとも１種であり、かつその
配合量が、紫外線硬化性樹脂１００重量部当たり３０〜
２００重量部である第(１)〜(６)項記載のソルダーフォ
トレジストインキ用組成物、及び、（８）熱硬化性樹脂
が、少なくとも２個の官能基を有する重合性化合物であ
り、かつその配合量が紫外線硬化性樹脂１００重量部当
たり５〜６０重量部である第(１)〜(７)項記載のソルダ
ーフォトレジストインキ用組成物。を提供するものであ
る。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid has two or more kinds. A composition containing an ultraviolet curable resin obtained by simultaneously reacting dibasic acids has excellent storage stability and dilute alkali developability, and the cured product has good mechanical properties.
They have found that they have chemical properties, and have completed the present invention based on this finding. That is, the present invention
(1) In a composition for a solder photoresist ink containing an ultraviolet-curable resin, a photopolymerization initiator, a diluent, and a thermosetting resin, the ultraviolet-curable resin is composed of a novolak-type epoxy compound and an unsaturated monocarboxylic acid. To the reaction product, a dibasic acid anhydride having a molecular weight of 120 or less and a dibasic acid anhydride having a molecular weight of 140 or more in a molar ratio of 1/9 to 9/1.
(2) The number of phenol nuclei of the novolak type epoxy compound is 4 to 8 nuclei on the average. (3) The composition for a solder photoresist ink according to the above (1),
The reaction of the epoxy group of the novolak type epoxy compound with an equivalent amount of an unsaturated monocarboxylic acid is carried out.
The composition for a solder photoresist ink according to any one of (1) to (2), (4) the ultraviolet curable resin is used in an amount of from 0.3 to 1 mol per mol of a hydroxyl group of a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid. (1) The composition for a solder photoresist ink according to any one of (1) to (3), which is obtained by reacting a dibasic acid anhydride with 1.0 mol, and (5) the ultraviolet curable resin is 40 to 100 mgKOH / g. (1) to (4), wherein the amount of the photopolymerization initiator is 0.2 per 100 parts by weight of the ultraviolet curable resin. The composition for solder photoresist ink according to any one of (1) to (5), wherein the diluent is at least one selected from an organic solvent and a photopolymerizable monomer. And the compounding amount is an ultraviolet curable resin. 00 parts by weight per 30
200 parts by weight of the composition for solder photoresist ink according to any one of (1) to (6), and (8) the thermosetting resin is a polymerizable compound having at least two functional groups, and The composition for solder photoresist ink according to any one of (1) to (7), wherein the compounding amount is 5 to 60 parts by weight per 100 parts by weight of the ultraviolet curable resin. Is provided.
【０００５】本発明のソルダーフォトレジストインキ用
組成物は、紫外線硬化性樹脂、光重合開始剤、希釈剤及
び熱硬化性樹脂を含有する組成物である。本発明に用い
る紫外線硬化性樹脂は、ノボラック型エポキシ化合物と
不飽和モノカルボン酸との反応生成物に、分子量が１２
０以下の二塩基酸無水物及び分子量が１４０以上の二塩
基酸無水物を、２種の二塩基酸無水物のモル比が１／９
〜９／１となる割合で同時に反応することにより得られ
るものである。使用するノボラック型エポキシ化合物
は、フェノール又はｏ−クレゾールなどとホルムアルデ
ヒドの反応生成物であるフェノールノボラック又はクレ
ゾールノボラックなどに、エピクロルヒドリンを反応す
ることにより得られる多官能のエポキシ化合物であり、
フェノール核の核数が平均４核以上８核以下であり、エ
ポキシ当量が１７０〜２３０であるものを好適に使用す
ることができる。フェノール核の核数が４核未満である
と、ソルダーフォトレジストインキ用組成物の硬化物が
脆くなるおそれがある。フェノール核の核数が８核を超
えると、ソルダーフォトレジストインキ用組成物の希ア
ルカリ現像性とポットライフが低下するおそれがある。
本発明においては、ノボラック型エポキシ化合物に不飽
和モノカルボン酸を反応する。エポキシ基とカルボキシ
ル基の反応により、オキシラン環が開環し、水酸基とエ
ステル結合が生成する。使用する不飽和モノカルボン酸
には特に制限はなく、アクリル酸、メタクリル酸、クロ
トン酸、ビニル酢酸、ソルビン酸、桂皮酸などを挙げる
ことができるが、アクリル酸は生成物の重合性が良好で
あり、硬化物の特性に優れるので、特に好適に使用する
ことができる。ノボラック型エポキシ化合物と不飽和モ
ノカルボン酸の反応方法には特に制限はなく、例えば、
ノボラック型エポキシ化合物と不飽和モノカルボン酸
を、適当な希釈剤中で加熱することにより反応すること
ができる。希釈剤としては、例えば、メチルエチルケト
ン、シクロヘキサノンなどのケトン類；トルエン、キシ
レンなど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などの脂環式炭化水
素類；石油エーテル、石油ナフサなどの石油系溶剤；セ
ロソルブ、ブチルセロソルブなどのセロソルブ類；カル
ビトール、ブチルカルビトールなどのカルビトール類；
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などの酢酸エステル類など
を挙げることができる。[0005] The composition for a solder photoresist ink of the present invention is a composition containing an ultraviolet curable resin, a photopolymerization initiator, a diluent, and a thermosetting resin. The ultraviolet curable resin used in the present invention has a molecular weight of 12 as a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid.
A dibasic anhydride having a molecular weight of 140 or less and a dibasic anhydride having a molecular weight of 140 or more are prepared by mixing the two dibasic anhydrides in a molar ratio of 1/9.
It is obtained by simultaneously reacting at a ratio of up to 9/1. The novolak type epoxy compound to be used is a polyfunctional epoxy compound obtained by reacting epichlorohydrin with phenol novolak or cresol novolak which is a reaction product of phenol or o-cresol or the like with formaldehyde,
A phenol nucleus having an average of 4 to 8 nuclei and an epoxy equivalent of 170 to 230 can be suitably used. If the number of phenol nuclei is less than 4, the cured product of the composition for solder photoresist ink may become brittle. If the number of phenol nuclei exceeds 8, the dilute alkali developability and pot life of the composition for solder photoresist ink may be reduced.
In the present invention, a novolak type epoxy compound is reacted with an unsaturated monocarboxylic acid. The oxirane ring is opened by the reaction between the epoxy group and the carboxyl group, and a hydroxyl group and an ester bond are formed. The unsaturated monocarboxylic acid to be used is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, sorbic acid, and cinnamic acid, and acrylic acid has good polymerizability of the product. Yes, the cured product has excellent properties, so that it can be used particularly preferably. The reaction method of the novolak type epoxy compound and the unsaturated monocarboxylic acid is not particularly limited, for example,
The novolak type epoxy compound and the unsaturated monocarboxylic acid can be reacted by heating 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; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Petroleum solvents such as petroleum ether and petroleum naphtha; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol;
Examples thereof include acetates such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, and butyl carbitol acetate.
【０００６】本発明において、反応するノボラック型エ
ポキシ化合物のエポキシ基の量と、不飽和モノカルボン
酸の量は、当量であることが好ましい。エポキシ基が過
剰であっても、不飽和モノカルボン酸が過剰であって
も、貯蔵安定性が低下し、硬化物の特性が低下するおそ
れがある。ノボラック型エポキシ化合物と不飽和モノカ
ルボン酸の反応温度は、９０〜２００℃であることが好
ましく、１００〜１３０℃であることがより好ましい。
ノボラック型エポキシ樹脂と不飽和モノカルボン酸の反
応に際しては、ノボラック型エポキシ化合物、不飽和モ
ノカルボン酸及び希釈剤よりなる反応混合物中の、ノボ
ラック型エポキシ化合物及び不飽和モノカルボン酸の合
計量が２０〜８０重量％であることが好ましい。ノボラ
ック型エポキシ化合物と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、希釈剤溶液のまま次の二塩
基酸無水物との反応に供することができる。本発明に用
いる紫外線硬化性樹脂は、ノボラック型エポキシ化合物
と不飽和モノカルボン酸の反応生成物に、分子量が１２
０以下の二塩基酸無水物及び分子量が１４０以上の二塩
基酸無水物を、２種の二塩基酸無水物のモル比が１／９
〜９／１となる割合で同時に反応することにより得られ
るものである。二塩基酸無水物としては、飽和二塩基酸
無水物及び不飽和二塩基酸無水物を使用することができ
る。分子量が１２０以下の二塩基酸無水物としては、例
えば、無水コハク酸、メチル無水コハク酸、無水グルタ
ル酸、無水マレイン酸、無水イタコン酸、無水グルタコ
ン酸、無水シトラコン酸、無水ジグリコール酸などを挙
げることができ、これらの中で無水コハク酸を特に好適
に使用することができる。分子量が１４０以上の二塩基
酸無水物としては、アリル無水コハク酸、無水フタル
酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタ
ル酸、メチルテトラヒドロ無水フタル酸、メチルヘキサ
ヒドロ無水フタル酸、エンドメチレンテトラヒドロ無水
フタル酸、メチルエンドメチレンテトラヒドロ無水フタ
ル酸、メチルブテニルテトラヒドロ無水フタル酸、無水
ジフェン酸、無水ニトロフタル酸、無水フタロン酸など
を挙げることができ、これらの中でテトラヒドロ無水フ
タル酸、メチルテトラヒドロ無水フタル酸及びエンドメ
チレンテトラヒドロ無水フタル酸を特に好適に使用する
ことができる。In the present invention, the amount of the epoxy group of the novolak epoxy compound to be reacted and the amount of the unsaturated monocarboxylic acid are preferably equivalent. Even if the epoxy group is excessive or the unsaturated monocarboxylic acid is excessive, the storage stability may be reduced and the properties of the cured product may be reduced. The reaction temperature between the novolak-type epoxy compound and the unsaturated monocarboxylic acid is preferably from 90 to 200C, more preferably from 100 to 130C.
In the reaction between the novolak type epoxy resin and the unsaturated monocarboxylic acid, the total amount of the novolak type epoxy compound and the unsaturated monocarboxylic acid in the reaction mixture comprising the novolak type epoxy compound, the unsaturated monocarboxylic acid and the diluent is 20. Preferably it is ~ 80% by weight. The reaction product of the novolak-type epoxy compound and the unsaturated monocarboxylic acid can be subjected to the next reaction with a dibasic acid anhydride without isolation, as a diluent solution. The ultraviolet curable resin used in the present invention has a molecular weight of 12 as a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid.
A dibasic anhydride having a molecular weight of 140 or less and a dibasic anhydride having a molecular weight of 140 or more are prepared by mixing the two dibasic anhydrides in a molar ratio of 1/9.
It is obtained by simultaneously reacting at a ratio of up to 9/1. As the dibasic acid anhydride, a saturated dibasic acid anhydride and an unsaturated dibasic acid anhydride can be used. Examples of the dibasic acid anhydride having a molecular weight of 120 or less include, for example, succinic anhydride, methyl succinic anhydride, glutaric anhydride, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, diglycolic anhydride, and the like. Among them, succinic anhydride can be particularly preferably used. As the dibasic anhydride having a molecular weight of 140 or more, allyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride Acid, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, diphenic anhydride, nitrophthalic anhydride, phthalonic anhydride, etc., among these, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride And endmethylenetetrahydrophthalic anhydride can be particularly preferably used.
【０００７】二塩基酸無水物は、ノボラック型エポキシ
化合物と不飽和モノカルボン酸との反応物が有する水酸
基と反応し、エステル結合と遊離のカルボキシル基を生
成する。ここで生成する遊離のカルボキシル基及びカル
ボキシル基の主鎖骨格との結合の状態が、希アルカリ現
像性、貯蔵安定性及び硬化塗膜の特性に強い影響を有し
ていて、分子量が１２０以下の二塩基酸無水物及び分子
量が１４０以上の二塩基酸無水物を、モル比が１／９〜
９／１となる割合で同時に反応することにより、好まし
くはモル比が３／７〜７／３となる割合で同時に反応す
ることにより、良好な性能を有する紫外線硬化性樹脂を
得ることができる。分子量が１２０以下の二塩基酸無水
物と分子量が１４０以上の二塩基酸無水物のモル比が１
／９未満であり、分子量が１２０以下の二塩基酸無水物
の割合が少ないと、希アルカリ現像性が低下するおそれ
がある。分子量が１２０以下の二塩基酸無水物と分子量
が１４０以上の二塩基酸無水物のモル比が９／１を超
え、分子量が１４０以上の二塩基酸無水物の割合が少な
いと、塗膜の良好な物性が十分発現しないおそれがあ
る。分子量が小さい二塩基酸無水物は、反応物の主鎖に
付加した状態でｐＫa値が比較的低く、希アルカリ現像
性向上に寄与する効果を有し、分子量が大きい二塩基酸
無水物は、反応物の主鎖に付加した状態でｐＫa値が比
較的高く、好適な電気特性、耐熱性に寄与する効果を有
するものと考えられる。The dibasic acid anhydride reacts with the hydroxyl group of the reaction product of the novolak type epoxy compound and the unsaturated monocarboxylic acid to generate an ester bond and a free carboxyl group. The state of the bond between the free carboxyl group and the main chain skeleton of the carboxyl group generated here has a strong influence on the properties of the diluted alkali developability, storage stability and the cured coating film, and the molecular weight is 120 or less. The dibasic acid anhydride and the dibasic acid anhydride having a molecular weight of 140 or more have a molar ratio of 1/9 to
By reacting at the same time at a ratio of 9/1, and preferably at the same time at a ratio of 3/7 to 7/3, an ultraviolet curable resin having good performance can be obtained. The molar ratio of a dibasic anhydride having a molecular weight of 120 or less to a dibasic anhydride having a molecular weight of 140 or more is 1
If the ratio of the dibasic acid anhydride having a molecular weight of 120 or less is small, the dilute alkali developability may be reduced. When the molar ratio of the dibasic acid anhydride having a molecular weight of 120 or less to the dibasic anhydride having a molecular weight of 140 or more exceeds 9/1, and the ratio of the dibasic anhydride having a molecular weight of 140 or more is small, the Good physical properties may not be sufficiently exhibited. A dibasic acid anhydride having a small molecular weight has a relatively low pKa value in a state of being added to the main chain of the reactant, and has an effect of contributing to improvement in dilute alkali developability. It is considered that the pK a value is relatively high in a state of being added to the main chain of the reactant, and has an effect of contributing to favorable electric characteristics and heat resistance.
【０００８】本発明に使用する紫外線硬化性樹脂におい
ては、分子量の異なる２種の二塩基酸無水物を、同時に
ノボラック型エポキシ化合物と不飽和モノカルボン酸の
反応生成物に添加して反応することが重要であり、この
ようにして得られる紫外線硬化性樹脂を含むフォトレジ
ストインキ用組成物は、優れた貯蔵安定性とソルダーフ
ォトレジストインキとしての良好な性能（光硬化性、希
アルカリ現像性、耐熱性、電気絶縁性、耐湿性）、なか
でも良好な希アルカリ現像性を兼ね備え、かつ良好な熱
硬化性を示す。上記の配合比を満足した上で、３種以上
の二塩基酸無水物を混合し反応せしめた場合も、得られ
る組成物は、貯蔵安定性及び希アルカリ現像性共に良好
である。しかし、２種の二塩基酸無水物をそれぞれ単独
でノボラック型エポキシ化合物と不飽和モノカルボン酸
の反応生成物と反応せしめて得た紫外線硬化性樹脂同士
を、後で混ぜあわせ配合しても、良好な貯蔵安定性及び
良好な希アルカリ現像性を兼ね備えた組成物は得られ
ず、熱硬化性も不良である。すなわち、ノボラック型エ
ポキシ化合物と不飽和モノカルボン酸の反応生成物に、
２種の二塩基酸無水物を逐次反応する場合も、また、ノ
ボラック型エポキシ化合物と不飽和モノカルボン酸の反
応生成物に分子量が１２０以下の二塩基酸無水物を反応
して得た樹脂と、ノボラック型エポキシ化合物と不飽和
モノカルボン酸の反応生成物に分子量が１４０以上の二
塩基酸無水物を反応して得た樹脂を混合して使用する場
合も、本発明の効果は得られない。その機構は明らかで
はないが、２種の二塩基酸無水物を同時に反応させるこ
とによって、紫外線硬化性樹脂中の同一分子に２種以上
の化学的に環境の異なるカルボキシル基が生成し、この
ことによって、単一の二塩基酸無水物を反応させた紫外
線硬化性樹脂では不可能であった優れた性能が、はじめ
て発現したものと考えられる。In the ultraviolet curable resin used in the present invention, two kinds of dibasic acid anhydrides having different molecular weights are simultaneously added to a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid to react. Is important, and the composition for a photoresist ink containing the ultraviolet curable resin obtained in this manner has excellent storage stability and good performance as a solder photoresist ink (photocurability, dilute alkali developability, (Heat resistance, electrical insulation, moisture resistance), among which good dilute alkali developability, and good thermosetting properties. Even when three or more dibasic acid anhydrides are mixed and reacted while satisfying the above mixing ratio, the resulting composition has good storage stability and dilute alkali developability. However, ultraviolet curable resins obtained by reacting two types of dibasic acid anhydrides alone with a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid may be mixed and compounded later. A composition having good storage stability and good dilute alkali developability cannot be obtained, and the thermosetting property is also poor. That is, the reaction product of the novolak type epoxy compound and the unsaturated monocarboxylic acid,
When two kinds of dibasic acid anhydrides are sequentially reacted, a resin obtained by reacting a reaction product of a novolak type epoxy compound with an unsaturated monocarboxylic acid with a dibasic acid anhydride having a molecular weight of 120 or less is also used. Even when a resin obtained by reacting a dibasic acid anhydride having a molecular weight of 140 or more with a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid is used, the effects of the present invention cannot be obtained. . Although the mechanism is not clear, the simultaneous reaction of two dibasic acid anhydrides produces two or more chemically different carboxyl groups in the same molecule in the UV-curable resin. Thus, it is considered that excellent performance, which was impossible with an ultraviolet curable resin obtained by reacting a single dibasic acid anhydride, was first exhibited.
【０００９】本発明に使用する紫外線硬化性樹脂の製造
においては、分子量が１２０以下の二塩基酸無水物を１
種使用することができ、２種以上を併用することができ
る。同様に、分子量が１４０以上の二塩基酸無水物を１
種使用することができ、２種以上を併用することができ
る。使用する二塩基酸無水物の種類が増加しても、分子
量が１２０以下の二塩基酸無水物と、分子量が１４０以
上の二塩基酸無水物のモル比が１／９〜９／１の範囲に
あれば、本発明の組成物に使用することができる。本発
明に使用する紫外線硬化性樹脂において、ノボラック型
エポキシ化合物と不飽和モノカルボン酸の反応生成物と
反応させる二塩基酸無水物の量は、ノボラック型エポキ
シ化合物と不飽和モノカルボン酸の反応生成物が有する
水酸基１モル当たり０.３〜１.０モルであることが好ま
しい。反応させる二塩基酸無水物の量が、ノボラック型
エポキシ化合物と不飽和モノカルボン酸の反応生成物が
有する水酸基１モル当たり０.３モル未満であると、希
アルカリ現像性及び塗膜の特性が低下するおそれがあ
る。反応させる二塩基酸無水物の量が、ノボラック型エ
ポキシ化合物と不飽和モノカルボン酸の反応生成物が有
する水酸基１モル当たり１.０モルを超えると、反応混
合物中に未反応の二塩基酸無水物が残存し、硬化した塗
膜の性能が低下する。In the production of the ultraviolet-curable resin used in the present invention, a dibasic acid anhydride having a molecular weight of 120 or less is used.
Species can be used, and two or more can be used in combination. Similarly, a dibasic anhydride having a molecular weight of 140 or more
Species can be used, and two or more can be used in combination. Even if the type of the dibasic anhydride used increases, the molar ratio of the dibasic anhydride having a molecular weight of 120 or less to the dibasic anhydride having a molecular weight of 140 or more is in the range of 1/9 to 9/1. Can be used for the composition of the present invention. In the ultraviolet curable resin used in the present invention, the amount of the dibasic anhydride to be reacted with the reaction product of the novolak type epoxy compound and the unsaturated monocarboxylic acid is determined by the amount of the reaction product of the novolak type epoxy compound and the unsaturated monocarboxylic acid. It is preferably from 0.3 to 1.0 mol per mol of the hydroxyl group of the product. When the amount of the dibasic acid anhydride to be reacted is less than 0.3 mol per 1 mol of the hydroxyl group of the reaction product of the novolak type epoxy compound and the unsaturated monocarboxylic acid, the diluted alkali developability and the properties of the coating film are reduced. It may decrease. If the amount of the dibasic acid anhydride to be reacted exceeds 1.0 mol per mol of the hydroxyl group of the reaction product of the novolak type epoxy compound and the unsaturated monocarboxylic acid, unreacted dibasic anhydride is added to the reaction mixture. The matter remains, and the performance of the cured coating film decreases.
【００１０】本発明に使用する紫外線硬化性樹脂におい
て、分子量が１２０以下の二塩基酸無水物及び分子量１
４０以上の二塩基酸無水物は、ノボラック型エポキシ化
合物と不飽和モノカルボン酸の反応生成物に同時に添加
して反応する。ノボラック型エポキシ化合物と不飽和モ
ノカルボン酸の反応生成物が希釈剤の溶液として存在す
るときは、この溶液に二塩基酸無水物の混合物を添加
し、加熱溶解して反応することにより、好適に反応を進
めることができる。ノボラック型エポキシ化合物と不飽
和モノカルボン酸の反応生成物と二塩基酸無水物を反応
する温度は、６０〜１２０℃であることが好ましく、７
０〜１００℃であることがより好ましい。本発明に使用
する紫外線硬化性樹脂は、酸価が４０〜１００mgKOH／
ｇであることが好ましい。得られる紫外線硬化性樹脂の
酸価は、反応する二塩基酸無水物の量を適当に選択する
ことにより、容易に調整することができる。紫外線硬化
性樹脂の酸価が４０mgKOH／ｇ未満であると、レジスト
組成物の希アルカリ現像性及び硬化した塗膜の密着性と
耐熱性が劣るおそれがある。紫外線硬化性樹脂の酸価が
１００mgKOH／ｇを超えると、硬化塗膜の耐熱性、耐湿
性及び電気絶縁性が劣るおそれがある。本発明のソルダ
ーフォトレジストインキ用組成物は、光重合開始剤を含
有する。使用する光重合開始剤に特に制限はなく、光照
射によって分解してラジカルを発生する従来公知のも
の、例えば、ベンゾイン類、ベンゾフェノン類、アセト
フェノン類、アントラキノン類、キサントン類、チオキ
サントン類又はケタール類などの中から選ばれた１種又
は２種以上が用いられる。このような光重合開始剤とし
ては、例えば、α−イソプロポキシ−α−フェニルアセ
トフェノン、α,α−ジメトキシ−α−フェニルアセト
フェノン、α,α−ジエトキシアセトフェノン、トリメ
チルベンゾイルホスフィンオキシド、１−フェニル−
１,２−プロパンジオン−２−ｏ−ベンゾイルオキシ
ム、１−フェニル−１,２−プロパンジオン−２−ｏ−
エトキシカルボニルオキシムなどを挙げることができ
る。また、これらの光重合開始剤は、公知の光重合促進
剤である安息香酸類、又は第３級アミン類などと組み合
わせて用いることができる。光重合開始剤の配合量の好
適な範囲は、紫外線硬化性樹脂１００重量部当たり０.
２〜２０.０重量部であることが好ましく、２.０〜１
０.０重量部であることがより好ましい。光重合開始剤
の配合量が、紫外線硬化性樹脂１００重量部当たり０.
２重量部未満であると、ソルダーフォトレジストインキ
用組成物の硬化に長時間の露光を必要とするおそれがあ
る。光重合開始剤の配合量が、紫外線硬化性樹脂１００
重量部当たり２０.０重量部を超えると、硬化した塗膜
の性能が低下するおそれがある。In the ultraviolet curable resin used in the present invention, a dibasic acid anhydride having a molecular weight of 120 or less and a molecular weight of 1
Forty or more dibasic acid anhydrides are simultaneously added to the reaction product of the novolak type epoxy compound and the unsaturated monocarboxylic acid to react. When the reaction product of the novolak-type epoxy compound and the unsaturated monocarboxylic acid is present as a solution of a diluent, a mixture of dibasic acid anhydride is added to this solution, and the mixture is heated and dissolved to react. The reaction can proceed. The temperature at which the reaction product of the novolak type epoxy compound and the unsaturated monocarboxylic acid reacts with the dibasic acid anhydride is preferably 60 to 120 ° C.,
The temperature is more preferably 0 to 100 ° C. The ultraviolet curable resin used in the present invention has an acid value of 40 to 100 mgKOH /
g is preferable. The acid value of the resulting ultraviolet-curable resin can be easily adjusted by appropriately selecting the amount of the dibasic acid anhydride that reacts. If the acid value of the ultraviolet-curable resin is less than 40 mgKOH / g, the resist composition may have poor alkali developability and poor adhesion and heat resistance of the cured coating film. If the acid value of the ultraviolet curable resin exceeds 100 mgKOH / g, the heat resistance, moisture resistance and electric insulation of the cured coating film may be poor. The composition for a solder photoresist ink of the present invention contains a photopolymerization initiator. There is no particular limitation on the photopolymerization initiator used, and conventionally known photopolymerization initiators that decompose by light irradiation to generate radicals, such as benzoins, benzophenones, acetophenones, anthraquinones, xanthones, thioxanthones, and ketals One or two or more selected from the above are used. Such photopolymerization initiators include, for example, α-isopropoxy-α-phenylacetophenone, α, α-dimethoxy-α-phenylacetophenone, α, α-diethoxyacetophenone, trimethylbenzoylphosphine oxide, 1-phenyl-
1,2-propanedione-2-o-benzoyl oxime, 1-phenyl-1,2-propanedione-2-o-
Ethoxycarbonyl oxime and the like can be mentioned. Further, these photopolymerization initiators can be used in combination with known photopolymerization accelerators such as benzoic acids or tertiary amines. The preferred range of the amount of the photopolymerization initiator is 0.2 per 100 parts by weight of the ultraviolet curable resin.
The amount is preferably 2 to 20.0 parts by weight, and 2.0 to 1 part by weight.
More preferably, the amount is 0.0 parts by weight. The compounding amount of the photopolymerization initiator is 0.1 per 100 parts by weight of the ultraviolet curable resin.
If the amount is less than 2 parts by weight, curing of the composition for a solder photoresist ink may require long exposure. When the blending amount of the photopolymerization initiator is 100
If the amount exceeds 20.0 parts by weight per part by weight, the performance of the cured coating film may be reduced.
【００１１】本発明のソルダーフォトレジストインキ用
組成物は、希釈剤を含有する。希釈剤としては、有機溶
剤又は光重合性モノマーを使用することができる。有機
溶剤を希釈剤として使用するときは、ノボラック型エポ
キシ化合物と不飽和モノカルボン酸の反応、及び、二塩
基酸無水物の反応による紫外線硬化性樹脂の合成に使用
した希釈剤をそのままソルダーフォトレジストインキ用
組成物の希釈剤とすることができる。必要に応じて、さ
らに有機溶剤を追加して、適当な濃度の組成物とするこ
とができる。光重合性モノマーは、熱重合性をも有する
場合が多いので、紫外線硬化性樹脂を合成したのち組成
物に配合することが好ましい。光重合性モノマーとして
は、例えば、メチル（メタ）アクリレート、エチル（メ
タ）アクリレート、ｎ−プロピル（メタ）アクリレー
ト、ｎ−ブチル（メタ）アクリレート、２−エチルヘキ
シル（メタ）アクリレート、ラウリル（メタ）アクリレ
ート、ステアリル（メタ）アクリレート、シクロヘキシ
ル（メタ）アクリレート、フェノキシエチル（メタ）ア
クリレート、２−エトキシエチル（メタ）アクリレー
ト、２−ブトキシエチル（メタ）アクリレート、グリシ
ジル（メタ）アクリレート、２−ヒドロキシエチル（メ
タ）アクリレート、２−ヒドロキシプロピル（メタ）ア
クリレート、ベンジル（メタ）アクリレート、エチレン
グリコールモノ（メタ）アクリレート、エチルカルビト
ール（メタ）アクリレートなどを代表とする単官能アク
リレート化合物；エチレングリコールジ（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ジ（メタ）アクリレート、
トリメチロールプロパンジ（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、グリセ
リンジグリシジルエーテルジ（メタ）アクリレート、グ
リセリントリグリシジルエーテルトリ（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、ペンタエリスリトールテトラ（メタ）アクリレー
ト、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、多官能エポキシアクリレート類などを代表とする多
官能アクリレートなどが挙げられる。ここにおいて（メ
タ）アクリレートはアクリレートとメタクリレートの両
者を示す。[0011] The composition for solder photoresist ink of the present invention contains a diluent. As a diluent, an organic solvent or a photopolymerizable monomer can be used. When an organic solvent is used as a diluent, the diluent used for the synthesis of the ultraviolet curable resin by the reaction of the novolak type epoxy compound and the unsaturated monocarboxylic acid, and the reaction of the dibasic acid anhydride is used as it is as the solder photoresist. It can be used as a diluent for the ink composition. If necessary, an organic solvent can be further added to obtain a composition having an appropriate concentration. Since the photopolymerizable monomer often also has a thermopolymerizability, it is preferable to blend the ultraviolet curable resin into the composition after synthesizing it. Examples of the photopolymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate. , Stearyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) ) Monofunctional acrylates represented by acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol mono (meth) acrylate, ethyl carbitol (meth) acrylate, etc. Relate compounds, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin diglycidyl ether di (meth) acrylate, glycerin triglycidyl ether tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( Examples thereof include polyfunctional acrylates represented by (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and polyfunctional epoxy acrylates. Here, (meth) acrylate indicates both acrylate and methacrylate.
【００１２】本発明のソルダーフォトレジストインキ用
組成物において、有機溶剤又は光重合性モノマーからな
る希釈剤の配合量は、紫外線硬化性樹脂１００重量部当
たり、３０〜２００重量部であることが好ましい。有機
溶剤は、紫外線硬化性樹脂合成時の溶媒として機能する
他に、ソルダーフォトレジストインキ用組成物をプリン
ト配線基板に塗布した後乾燥させることによって造膜さ
せるために用いる。光重合性モノマーは、ソルダーフォ
トレジストインキ用組成物を希釈し、塗布しやすい粘度
にするために用いる他に、光重合性を促進するために使
用する。希釈剤の配合量が紫外線硬化性樹脂１００重量
部当たり３０重量部未満であると、ソルダーフォトレジ
ストインキ用組成物の粘度が高く、プリント配線基板へ
の塗布が困難になるおそれがある。希釈剤の配合量が紫
外線硬化性樹脂１００重量部当たり２００重量部を超え
ると、ソルダーフォトレジストインキ用組成物の粘度が
低くなりすぎて塗布が困難になり、希釈剤が有機溶剤で
ある場合はタックフリーまで乾燥するのに時間がかか
り、希釈剤が光重合性モノマーである場合には硬化した
塗膜の性能が低下するおそれがある。In the solder photoresist ink composition of the present invention, the compounding amount of the diluent comprising an organic solvent or a photopolymerizable monomer is preferably 30 to 200 parts by weight per 100 parts by weight of the ultraviolet curable resin. . The organic solvent functions not only as a solvent when synthesizing the ultraviolet curable resin, but also used for forming a film by applying a composition for a solder photoresist ink to a printed wiring board and then drying the composition. The photopolymerizable monomer is used not only for diluting the composition for solder photoresist ink to have a viscosity that facilitates application, but also for promoting photopolymerizability. When the compounding amount of the diluent is less than 30 parts by weight per 100 parts by weight of the ultraviolet curable resin, the viscosity of the composition for a solder photoresist ink is high, and it may be difficult to apply the composition to a printed wiring board. When the compounding amount of the diluent exceeds 200 parts by weight per 100 parts by weight of the ultraviolet curable resin, the viscosity of the composition for the solder photoresist ink becomes too low to make application difficult, and when the diluent is an organic solvent, It takes time to dry to tack-free, and when the diluent is a photopolymerizable monomer, the performance of the cured coating film may be reduced.
【００１３】本発明のソルダーフォトレジストインキ用
組成物には、熱硬化性樹脂を配合する。熱硬化性樹脂
は、紫外線線硬化性樹脂中に残存するカルボキシル基を
封鎖し、ソルダーレジストの必須性能である、密着性、
耐熱性、電気絶縁性、耐湿性を向上させる。熱硬化性樹
脂としては、公知の２官能以上の各種エポキシ樹脂、ウ
レタン樹脂などを用いることができるが、平均して４官
能以上８官能以下のエポキシ樹脂を特に好適に使用する
ことができる。本発明のソルダーフォトレジストインキ
用組成物において、熱硬化性樹脂は紫外線硬化性樹脂１
００重量部当たり５〜６０重量部を配合することが好ま
しく、１０〜４０重量部を配合することがより好まし
い。熱硬化性樹脂の配合量が紫外線硬化性樹脂１００重
量部当たり５重量部未満であると、硬化した塗膜の密着
性と耐熱性が低下するおそれがある。熱硬化性樹脂の配
合量が紫外線硬化性樹脂１００重量部当たり６０重量部
を超えると、希アルカリ現像性が低下するおそれがあ
る。熱硬性化樹脂の熱硬化反応を促進するために、イミ
ダゾール類、アミン化合物、カルボン酸類、フェノール
類、第４級アンモニウム塩類、メチルロール基含有化合
物などの公知の硬化促進剤を併用することができる。本
発明のソルダーフォトレジストインキ用組成物の調製に
際しては、増粘、ひいては希アルカリ現像性の低下を避
けるため、熱硬化性樹脂は、プリント配線基板に塗布す
る直前に、他のソルダーフォトレジスト組成物の必須成
分と混合し配合することが好ましい。The composition for a solder photoresist ink of the present invention contains a thermosetting resin. The thermosetting resin blocks the carboxyl groups remaining in the ultraviolet ray curable resin, and is an essential property of solder resist, adhesion,
Improves heat resistance, electrical insulation, and moisture resistance. As the thermosetting resin, various known bifunctional or higher functional epoxy resins, urethane resins, and the like can be used, and an average of 4 functional to 8 functional epoxy resins can be particularly preferably used. In the composition for a solder photoresist ink of the present invention, the thermosetting resin is an ultraviolet curable resin 1
It is preferable to blend 5 to 60 parts by weight, more preferably 10 to 40 parts by weight, per 100 parts by weight. When the compounding amount of the thermosetting resin is less than 5 parts by weight per 100 parts by weight of the ultraviolet curable resin, the adhesion and heat resistance of the cured coating film may be reduced. When the compounding amount of the thermosetting resin exceeds 60 parts by weight per 100 parts by weight of the ultraviolet curable resin, the dilute alkali developability may be reduced. In order to accelerate the thermosetting reaction of the thermosetting resin, a known curing accelerator such as an imidazole, an amine compound, a carboxylic acid, a phenol, a quaternary ammonium salt, or a compound having a methylol group can be used in combination. . In preparing the composition for a solder photoresist ink of the present invention, in order to avoid thickening and, consequently, decrease in dilute alkali developability, a thermosetting resin is used immediately before application to a printed wiring board. It is preferable to mix and mix the essential components of the product.
【００１４】本発明のソルダーフォトレジストインキ用
組成物においては、必要に応じて、硫酸バリウム、酸化
ケイ素などの公知の充填剤、フタロシアニングリーン、
フタロシアニンブルー、二酸化チタン、カーボンブラッ
クなどの公知の着色用顔料、消泡剤、レベリング剤など
の各種添加剤、あるいはハイドロキノン、ハイドロキノ
ンモノメチルエーテル、ピロガロール、ｔ−ブチルカテ
コールなどの公知の重合禁止剤などを配合することがで
きる。本発明のソルダーフォトレジストインキ用組成物
をプリント配線基板に適用する方法には特に制限はな
く、例えば、プリント配線基板上にスクリーン印刷法、
ロールコーター法、スプレー法、あるいはカーテンコー
ター法などにより全面に塗布し、６５〜８０℃で乾燥さ
せ表面の粘着性（タック）を除去した上で、フォトマス
クなどで不必要な部分をマスクし、光硬化を行ったの
ち、希アルカリ水溶液で未露光部分を溶解し、さらに熱
硬化を行うことによりソルダーレジスト硬化塗膜を得る
ことができる。本発明のソルダーフォトレジストインキ
用組成物の光硬化のための照射光源としては、公知の光
源を使用することができ、このような光源としては、例
えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水
銀灯、キセノンランプあるいはメタルハライドランプな
どを挙げることができる。In the composition for a solder photoresist ink of the present invention, if necessary, a known filler such as barium sulfate or silicon oxide, phthalocyanine green,
Known coloring pigments such as phthalocyanine blue, titanium dioxide, and carbon black, various additives such as antifoaming agents, leveling agents, or known polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol. Can be blended. The method for applying the composition for a solder photoresist ink of the present invention to a printed wiring board is not particularly limited, for example, a screen printing method on a printed wiring board,
After applying the whole surface by a roll coater method, a spray method, a curtain coater method or the like, drying at 65 to 80 ° C. to remove the tackiness (tack) on the surface, masking unnecessary portions with a photomask or the like, After photo-curing, the unexposed portion is dissolved with a dilute alkali aqueous solution, and further heat-cured to obtain a solder resist cured coating film. Known light sources can be used as the irradiation light source for photocuring the solder photoresist ink composition of the present invention. Examples of such light sources include a low-pressure mercury lamp, a medium-pressure mercury lamp, and a high-pressure mercury lamp. An ultra-high pressure mercury lamp, a xenon lamp or a metal halide lamp can be used.
【００１５】[0015]
【実施例】以下に、実施例を挙げて本発明をさらに詳細
に説明するが、本発明はこれらの実施例によりなんら限
定されるものではない。なお、紫外線硬化性樹脂のシェ
ルフライフ、組成物の現像性及び塗膜性能は下記の方法
により評価した。 （１）紫外線硬化性樹脂のシェルフライフ促進試験 紫外線硬化性樹脂をふた付きのプラスチック製のビンに
入れ、６０℃の恒温槽に浸漬し、２５℃における粘度が
初期粘度の２.５倍に達するか、あるいは１,０００ポイ
ズを超えるまでの日数で評価した。 （２）希アルカリ現像性 テスト用プリント配線基板製作過程において、光照射に
よる硬化後に１重量％炭酸ナトリウム水溶液を現像液と
して用い、２０℃でスターラー撹拌により現像した際の
現像性を、次に示す基準により評価した。 ◎：１分以内で現像可能。 ○：１分を超え３分以内で現像可能。 △：３分を超え５分以内で現像可能。 ×：５分以内で現像不可能。 なお、仮乾燥状態におけるソルダーフォトレジストイン
キの安定性を評価するため、７５℃で３０分間仮乾燥を
行い、その直後と仮乾燥３日後の両方について、現像性
を評価した。 （３）密着性 ＪＩＳ Ｋ ５４００ ８.５.２に準じて、それぞれのテ
スト用プリント配線基板に碁盤目状に縦横１０本のクロ
スカットを入れ、次いでセロハンテープによる剥離試験
後の塗膜の剥離状態を目視によって判定した。 ◎：１００／１００で全く剥離が認められないもの。 ○：１００／１００で線の際がわずかにはがれたもの。 △：９０／１００〜９９／１００。 ×：０／１００〜８９／１００。 （４）鉛筆硬度 ＪＩＳ Ｋ ５４００ ８.４.２に準じて、「三菱ユニ」
鉛筆を用い、塗膜に傷が付かない最も高い硬度をもって
評価した。 （５）はんだ耐熱性 テスト用プリント配線基板に、ロジン系フラックス
［(株)アサヒ化学研究所、商品名 ＧＸ−７］を塗布
し、２６０℃に保ったはんだ浴に塗膜面をはんだに接触
するようにして１５秒間浮かべ、その後塗膜の膨れと剥
離を観察した。これを１サイクルとし、膨れ又は剥離が
生ずるまでの延べ時間により評価した。 （６）耐水溶性フラックス性 それぞれのテスト用プリント配線基板に、水溶性フラッ
クス［ＬＯＮＣＯ社、商品名 ＣＦ−３５０］を塗布
し、２６０℃のはんだ浴に塗膜面をはんだに接触するよ
うにして５秒間浮かべ、さらに６０℃の温水に１５分間
浸漬したのち、セロハンテープにより剥離試験を行っ
た。同時に塗膜表面の光沢の変化、特に白化状態を観察
した。評価基準を以下に示す。 剥離試験 ◎：全くはがれないもの。 ○：ほんのわずかにはがれたもの。 △：全体の１０〜３０％がはがれたもの。 ×：全体の３１％以上がはがれたもの。 白化状態 ◎：全く白化していないもの。 ○：ほんのわずかに白化しているもの。 △：全体の１０〜３０％が白化しているもの。 ×：全体の３１％以上が白化しているもの。 （７）電気絶縁性試験 ＪＩＳ Ｚ ３１９７に準じて、それぞれのテスト用プリ
ント配線基板について初期の絶縁性と、６０℃、相対湿
度９０％に５００時間放置したのちの絶縁性とを、ＳＭ
−８２１０［東亜電波(株)製］を用いてＤＣ５００Ｖで
の１分値として評価した。 製造例１（紫外線硬化性樹脂の製造） 撹拌機、還流冷却管、滴下ロート及び温度計を備えた１
リットル容のセパラブルフラスコに、エチルカルビトー
ルアセテート１９０ｇ及びエポキシ当量が２１５で１分
子中に平均して６個のフェノール核を有するクレゾール
ノボラック型エポキシ樹脂２１５ｇを仕込んだ。撹拌し
つつ１２０℃まで加熱し、１２０℃を保ったまま滴下ロ
ートよりアクリル酸７２ｇ（１.０モル）を１時間かけ
て滴下し、さらに１０時間１２０℃で反応を続けた。い
ったん反応混合物を室温まで冷却し、無水コハク酸２０
ｇ（０.２モル）及びテトラヒドロ無水フタル酸４６ｇ
（０.３モル）を加え、ふたたび８０℃に加熱して３時
間反応した。反応終了後、室温まで冷却したところ、粘
稠な溶液が得られた。この溶液の加熱残分は６５重量％
であり、溶液として５３mgKOH／ｇの酸価を示した。こ
の溶液を、樹脂Ａ−１とする。 製造例２（紫外線硬化性樹脂の製造） 製造例１のエチルカルビトールアセテート１９０ｇの代
わりに、カルビトールアセテート１９８ｇを用い、無水
コハク酸２０ｇ及びテトラヒドロ無水フタル酸４６ｇの
代わりに、無水コハク酸３０ｇ（０.３モル）及びメチ
ルテトラヒドロ無水フタル酸５０ｇ（０.３モル）を用
いた以外は、製造例１と同じ操作を繰り返した。得られ
た粘稠な溶液の加熱残分は６５重量％であり、溶液とし
て６０mgKOH／ｇの酸価を示した。この溶液を、樹脂Ａ
−２とする。 製造例３（紫外線硬化性樹脂の製造） 製造例１のエチルカルビトールアセテート１８８ｇの代
わりに、ブチルセロソルブ１９５ｇを用い、無水コハク
酸２０ｇ及びテトラヒドロ無水フタル酸４６ｇの代わり
に、無水コハク酸３０ｇ（０.３モル）、テトラヒドロ
無水フタル酸３０ｇ（０.２モル）及びエンドメチレン
テトラヒドロ無水フタル酸１６ｇ（０.１モル）を用い
た以外は、製造例１と同じ操作を繰り返した。得られた
粘稠な溶液の加熱残分は６５重量％であり、溶液として
６１mgKOH／ｇの酸価を示した。この溶液を、樹脂Ａ−
３とする。 参考例１（紫外線硬化性樹脂の製造） 製造例１のエチルカルビトールアセテートの量を１８１
ｇとし、無水コハク酸２５ｇ及びテトラヒドロ無水フタ
ル酸３８ｇの代わりに、無水コハク酸５０ｇ（０.５モ
ル）を用いた以外は、製造例１と同じ操作を繰り返し
た。得られた粘稠な溶液の加熱残分は６５重量％であ
り、溶液として５７mgKOH／ｇの酸価を示した。この溶
液を、樹脂Ａ−４とする。 参考例２（紫外線硬化性樹脂の製造） 製造例１のエチルカルビトールアセテートの量を１９５
ｇとし、無水コハク酸２５ｇ及びテトラヒドロ無水フタ
ル酸３８ｇの代わりに、テトラヒドロ無水フタル酸７６
ｇ（０.５モル）を用いた以外は、製造例１と同じ操作
を繰り返した。得られた粘稠な溶液の加熱残分は６５重
量％であり、溶液として４９mgKOH／ｇの酸価を示し
た。この溶液を、樹脂Ａ−５とする。 参考例３（紫外線硬化性樹脂の製造） 樹脂Ａ−４と樹脂Ａ−５を重量比１：１で混合した。得
られた粘稠な溶液の加熱残分は６５重量％であり、溶液
として５３mgKOH／ｇの酸価を示した。この溶液を、樹
脂Ａ−６とする。製造例１〜３の紫外線硬化性樹脂Ａ−
１〜３及び参考例１〜３の紫外線硬化性樹脂Ａ−４〜６
について、シェルフライフ促進試験を行った。結果を第
２表に示す。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The shelf life of the ultraviolet curable resin, the developability of the composition, and the performance of the coating film were evaluated by the following methods. (1) Shelf life promotion test of UV-curable resin Put UV-curable resin into a plastic bottle with a lid and immerse it in a thermostat at 60 ° C. The viscosity at 25 ° C reaches 2.5 times the initial viscosity. Or the number of days until exceeding 1,000 poise. (2) Dilute Alkaline Developability In the process of manufacturing a test printed wiring board, the developability of a 1% by weight aqueous solution of sodium carbonate as a developing solution after being cured by light irradiation and development by stirring with a stirrer at 20 ° C. is shown below. The evaluation was based on criteria. A: Developable within 1 minute. ○: Developable in more than 1 minute and within 3 minutes. Δ: Developable in more than 3 minutes and within 5 minutes. X: Development was impossible within 5 minutes. In order to evaluate the stability of the solder photoresist ink in the temporarily dried state, temporary drying was performed at 75 ° C. for 30 minutes, and the developability was evaluated both immediately and three days after the temporary drying. (3) Adhesion In accordance with JIS K 5400 8.5.2., Each test printed wiring board is cut into 10 crosscuts vertically and horizontally in a checkerboard pattern, and then the coating film is peeled off after a peeling test using a cellophane tape. The state was visually determined. ◎: No peeling was observed at 100/100. ：: 100/100, the line was slightly peeled off. Δ: 90/100 to 99/100. ×: 0/100 to 89/100. (4) Pencil hardness “Mitsubishi Uni” according to JIS K 5400 8.4.2
Using a pencil, evaluation was made with the highest hardness that would not damage the coating film. (5) Solder heat resistance A rosin-based flux [Asahi Chemical Laboratory Co., Ltd., trade name: GX-7] is applied to the test printed wiring board, and the coating surface is brought into contact with the solder in a solder bath maintained at 260 ° C. Then, the film was floated for 15 seconds, and then the blistering and peeling of the coating film were observed. This was defined as one cycle, and the evaluation was made based on the total time until blistering or peeling occurred. (6) Water-soluble flux resistance A water-soluble flux [LONCO, trade name: CF-350] is applied to each test printed wiring board, and the coating surface is brought into contact with the solder in a 260 ° C. solder bath. After floating for 5 seconds and further immersion in 60 ° C. warm water for 15 minutes, a peeling test was carried out using cellophane tape. At the same time, a change in gloss on the surface of the coating film, particularly, a whitening state was observed. The evaluation criteria are shown below. Peeling test ◎: No peeling. ：: Slightly peeled off. Δ: 10 to 30% of the whole peeled off. X: 31% or more of the whole was peeled off. Whitening state A: Not whitened at all. ：: Only slightly whitened. Fair: 10 to 30% of the whole is whitened. X: 31% or more of the whole is whitened. (7) Electrical Insulation Test According to JIS Z 3197, the initial insulation property of each test printed circuit board and the insulation property after being left at 60 ° C. and a relative humidity of 90% for 500 hours were measured using SM.
It was evaluated as a 1-minute value at DC 500 V using −8210 [manufactured by Toa Denpa Co., Ltd.]. Production Example 1 (Production of UV-curable resin) 1 equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer
A liter separable flask was charged with 190 g of ethyl carbitol acetate and 215 g of a cresol novolak type epoxy resin having an epoxy equivalent of 215 and having an average of 6 phenol nuclei in one molecule. The mixture was heated to 120 ° C. with stirring, and while maintaining the temperature at 120 ° C., 72 g (1.0 mol) of acrylic acid was added dropwise from the dropping funnel over 1 hour, and the reaction was continued at 120 ° C. for 10 hours. Once the reaction mixture has cooled to room temperature, succinic anhydride 20
g (0.2 mol) and 46 g of tetrahydrophthalic anhydride
(0.3 mol), and the mixture was heated again to 80 ° C. and reacted for 3 hours. After the completion of the reaction, the mixture was cooled to room temperature to obtain a viscous solution. The heating residue of this solution is 65% by weight.
The solution showed an acid value of 53 mgKOH / g. This solution is referred to as resin A-1. Production Example 2 (Production of UV curable resin) Instead of 190 g of ethyl carbitol acetate of Production Example 1, 198 g of carbitol acetate was used, and instead of 20 g of succinic anhydride and 46 g of tetrahydrophthalic anhydride, 30 g of succinic anhydride ( 0.3 mol) and 50 g (0.3 mol) of methyltetrahydrophthalic anhydride, and the same operation as in Production Example 1 was repeated. The heating residue of the obtained viscous solution was 65% by weight, and the solution showed an acid value of 60 mgKOH / g. This solution is mixed with resin A
-2. Production Example 3 (Production of UV-curable resin) Instead of 188 g of ethyl carbitol acetate of Production Example 1, 195 g of butyl cellosolve was used, and instead of 20 g of succinic anhydride and 46 g of tetrahydrophthalic anhydride, 30 g of succinic anhydride (0.1 g) was used. 3 mol), 30 g (0.2 mol) of tetrahydrophthalic anhydride and 16 g (0.1 mol) of endmethylenetetrahydrophthalic anhydride were used, and the same operation as in Production Example 1 was repeated. The heating residue of the obtained viscous solution was 65% by weight, and the solution showed an acid value of 61 mgKOH / g. This solution was added to resin A-
3 is assumed. Reference Example 1 (Production of UV-curable resin) The amount of ethyl carbitol acetate in Production Example 1 was 181.
g, and the same operation as in Production Example 1 was repeated except that 50 g (0.5 mol) of succinic anhydride was used instead of 25 g of succinic anhydride and 38 g of tetrahydrophthalic anhydride. The heating residue of the obtained viscous solution was 65% by weight, and the solution showed an acid value of 57 mgKOH / g. This solution is referred to as resin A-4. Reference Example 2 (Production of UV-curable resin) The amount of ethyl carbitol acetate in Production Example 1 was 195.
g, and instead of 25 g of succinic anhydride and 38 g of tetrahydrophthalic anhydride, 76 g of tetrahydrophthalic anhydride was used.
The same operation as in Production Example 1 was repeated except that g (0.5 mol) was used. The heating residue of the obtained viscous solution was 65% by weight, and the solution showed an acid value of 49 mgKOH / g. This solution is referred to as resin A-5. Reference Example 3 (Production of UV-curable resin) Resin A-4 and resin A-5 were mixed at a weight ratio of 1: 1. The heating residue of the obtained viscous solution was 65% by weight, and the solution showed an acid value of 53 mgKOH / g. This solution is referred to as resin A-6. UV curable resin A of Production Examples 1 to 3
UV curable resins A-4 to 6 of Reference Examples 1-3 and Reference Examples 1-3
Was subjected to a shelf life promotion test. The results are shown in Table 2.
【００１６】実施例１ 紫外線硬化性樹脂Ａ−１を５５ｇ、光重合開始剤［チバ
・ガイギー社、イルガキュアー９０７］３ｇ、光重合開
始剤［日本化薬(株)、Ｃａｙａｃｕｒｅ ＤＥＴＸ−
Ｓ］１ｇ、希釈剤としてのトリメチロールプロパントリ
アクリレート５ｇ、イミダゾール系熱硬化剤［日本合成
化学工業(株)、ニチゴーイミダゾール２ＭＩ−ＡＺ］
０.５ｇ、フタロシアニングリーン顔料３ｇ、硫酸バリ
ウム１２ｇ、酸化ケイ素１０ｇ及び消泡剤［日華化学
(株)、フォームレックスＳＯＬ−３０］０.５ｇを、ロ
ールミル（３本ロール）により混練したのち、熱硬化性
樹脂としてｏ−クレゾールノボラック型エポキシ樹脂
［東都化成(株)、ＹＤＣＮ−７０２Ｓ］１０ｇを混合し
て、ソルダーフォトレジストインキ用組成物を調製し
た。この組成物を、あらかじめエッチングしてパターン
を形成しておいた銅プリント配線基板２枚にスクリーン
印刷法にて１５〜２０μｍの膜厚で全面に塗布し、熱風
循環型乾燥炉で７５℃で３０分仮乾燥した。仮乾燥直後
に、基板のうち１枚にフォトマスクを当て、３ｋＷメタ
ルハライドランプにより紫外線５００ｍＪ／cm2を照射
し、光硬化を行った。次いで１重量％炭酸ナトリウム水
溶液を現像液として用い、塗膜の未硬化部分を除去し
た。現像した基板は、さらに１５０℃で３０分間熱硬化
を行い、テスト用プリント配線基板を完成した。テスト
用基板の他の１枚は、仮乾燥を行った３日後に紫外線露
光を上記の条件で行い、同様に炭酸ナトリウム水溶液で
現像し、さらに熱硬化を行った。仮乾燥直後の現像性
と、仮乾燥３日後の現像性を評価した。仮乾燥直後に露
光及び現像を行ったテスト用プリント配線基板を用い
て、塗膜の性能評価を行った。結果を第２表に示す。 実施例２ 紫外線硬化性樹脂として樹脂Ａ−２を用いた以外は、実
施例１と全く同じ操作を繰り返し、テスト用プリント配
線基板を作成した。希アルカリ現像性及び塗膜性能を評
価し、結果を第２表に示した。 実施例３ 紫外線硬化性樹脂として樹脂Ａ−３を用いた以外は、実
施例１と全く同じ操作を繰り返し、テスト用プリント配
線基板を作成した。希アルカリ現像性及び塗膜性能を評
価し、結果を第２表に示した。 比較例１ 紫外線硬化性樹脂として樹脂Ａ−４を用いた以外は、実
施例１と全く同じ操作を繰り返し、テスト用プリント配
線基板を作成した。希アルカリ現像性及び塗膜性能を評
価し、結果を第２表に示した。 比較例２ 紫外線硬化性樹脂として樹脂Ａ−５を用いた以外は、実
施例１と全く同じ操作を繰り返し、テスト用プリント配
線基板を作成した。希アルカリ現像性及び塗膜性能を評
価し、結果を第２表に示した。 比較例３ 紫外線硬化性樹脂として樹脂Ａ−６を用いた以外は、実
施例１と全く同じ操作を繰り返し、テスト用プリント配
線基板を作成した。希アルカリ現像性及び塗膜性能を評
価し、結果を第２表に示した。Example 1 55 g of an ultraviolet curable resin A-1, 3 g of a photopolymerization initiator [Circa Geigy, Irgacure 907], and a photopolymerization initiator [Cyacure DETX-, Nippon Kayaku Co., Ltd.]
S] 1 g, trimethylolpropane triacrylate 5 g as a diluent, imidazole-based thermosetting agent [Nippon Synthetic Chemical Industry Co., Ltd., Nichigo imidazole 2MI-AZ]
0.5 g, phthalocyanine green pigment 3 g, barium sulfate 12 g, silicon oxide 10 g and defoamer [Nichika Chemical
(Form Co., Ltd., Formrex SOL-30) is kneaded with a roll mill (three rolls), and then 10 g of an o-cresol novolak epoxy resin [Toto Kasei Co., Ltd., YDCN-702S] is used as a thermosetting resin. Was mixed to prepare a composition for solder photoresist ink. This composition is applied to the entire surface of two copper printed wiring boards having a pattern formed by etching in advance in a thickness of 15 to 20 μm by a screen printing method, and heated at 75 ° C. in a hot air circulation type drying oven at 30 ° C. Temporarily dried. Immediately after the preliminary drying, one of the substrates was covered with a photomask, and irradiated with ultraviolet rays at 500 mJ / cm 2 from a 3 kW metal halide lamp to perform photocuring. Next, an uncured portion of the coating film was removed using a 1% by weight aqueous solution of sodium carbonate as a developing solution. The developed substrate was further thermally cured at 150 ° C. for 30 minutes to complete a test printed wiring board. Three days after the preliminary drying, the other one of the test substrates was exposed to ultraviolet light under the above conditions, similarly developed with an aqueous sodium carbonate solution, and further thermally cured. The developability immediately after temporary drying and the developability three days after temporary drying were evaluated. The performance of the coating film was evaluated using the test printed wiring board that was exposed and developed immediately after the preliminary drying. The results are shown in Table 2. Example 2 The same operation as in Example 1 was repeated except that the resin A-2 was used as the ultraviolet-curable resin, to prepare a test printed wiring board. The dilute alkali developability and coating film performance were evaluated, and the results are shown in Table 2. Example 3 The same operation as in Example 1 was repeated except that the resin A-3 was used as the ultraviolet-curable resin, to prepare a test printed wiring board. The dilute alkali developability and coating film performance were evaluated, and the results are shown in Table 2. Comparative Example 1 The same operation as in Example 1 was repeated except that the resin A-4 was used as the ultraviolet-curable resin, to prepare a test printed wiring board. The dilute alkali developability and coating film performance were evaluated, and the results are shown in Table 2. Comparative Example 2 The same operation as in Example 1 was repeated, except that the resin A-5 was used as the ultraviolet-curable resin, to prepare a test printed wiring board. The dilute alkali developability and coating film performance were evaluated, and the results are shown in Table 2. Comparative Example 3 The same operation as in Example 1 was repeated, except that the resin A-6 was used as the ultraviolet-curable resin, to prepare a test printed wiring board. The dilute alkali developability and coating film performance were evaluated, and the results are shown in Table 2.
【００１７】[0017]
【表１】 [Table 1]
【００１８】［注］１）チバ・ガイギー社製の光重合開
始剤。 ２）日本化薬(株)製の光重合開始剤。 ３）日本合成化学工業(株)製のイミダゾール系熱硬化
剤。 ４）日華化学(株)製の消泡剤。 ５）東都化成(株)製のｏ−クレゾールノボラック型エポ
キシ樹脂。[Note] 1) A photopolymerization initiator manufactured by Ciba Geigy. 2) Photopolymerization initiator manufactured by Nippon Kayaku Co., Ltd. 3) An imidazole-based thermosetting agent manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 4) Antifoaming agent manufactured by Nika Chemical Co., Ltd. 5) o-cresol novolak type epoxy resin manufactured by Toto Kasei Co., Ltd.
【００１９】[0019]
【表２】 [Table 2]
【００２０】本発明に使用する製造例１、２及び３で製
造した紫外線硬化性樹脂は、促進試験におけるシェルフ
ライフが長く、良好な貯蔵安定性を示している。これに
対して、分子量１００の無水コハク酸のみを使用した参
考例１の紫外線硬化性樹脂、及び、分子量１００の無水
コハク酸のみを使用した紫外線硬化性樹脂と分子量１５
２のテトラヒドロ無水フタル酸のみを使用した紫外線硬
化性樹脂を配合した参考例３の紫外線硬化性樹脂は、促
進試験におけるシェルフライフが短く、貯蔵安定性に劣
ることが分かる。実施例１〜３の本発明のソルダーフォ
トレジストインキ用組成物は、仮乾燥直後には希アルカ
リ現像性に優れ、仮乾燥３日後においても優秀ないし良
好な希アルカリ現像性を示している。また、実施例１〜
３の本発明のソルダーフォトレジストインキ用組成物か
ら得られた塗膜は、密着性、鉛筆硬度、はんだ耐熱性、
耐水溶性フラックス性及び電気絶縁性のすべてについ
て、優秀ないし良好な性能を示している。これに対し
て、分子量が１００である無水コハク酸のみを用いて製
造した紫外線硬化性樹脂を使用した比較例１のソルダー
フォトレジストインキ用組成物は、仮乾燥３日後の希ア
ルカリ現像性が不良であり、はんだ耐熱性、耐水溶性フ
ラックス性と電気絶縁性に劣る。分子量が１５２である
テトラヒドロ無水フタル酸のみを用いて製造した紫外線
硬化性樹脂を使用した比較例２のソルダーフォトレジス
トインキ用組成物は、希アルカリ現像性に劣っている。
無水コハク酸のみを用いて製造した紫外線硬化性樹脂
と、テトラヒドロ無水フタル酸のみを用いて製造した紫
外線硬化性樹脂の混合物を使用した比較例３のソルダー
フォトレジストインキ用組成物は、紫外線硬化性樹脂中
の無水コハク酸の量とテトラヒドロ無水フタル酸の量の
比は本発明の範囲内にあるにもかかわらず、それらを同
時に反応したものではないために、希アルカリ現像性に
劣り、密着性、はんだ耐熱性、耐水溶性フラックス性、
電気絶縁性に劣っている。The ultraviolet curable resins produced in Production Examples 1, 2 and 3 used in the present invention have a long shelf life in an accelerated test and show good storage stability. In contrast, the UV curable resin of Reference Example 1 using only succinic anhydride having a molecular weight of 100, and the UV curable resin using only succinic anhydride having a molecular weight of 100 and a molecular weight of 15
It can be seen that the UV curable resin of Reference Example 3, in which the UV curable resin using only tetrahydrophthalic anhydride of No. 2 was blended, had a short shelf life in the accelerated test and was inferior in storage stability. The compositions for solder photoresist inks of the present invention of Examples 1 to 3 have excellent dilute alkali developability immediately after preliminary drying, and show excellent or good dilute alkali developability even after three days of preliminary drying. Further, Examples 1 to
3, the coating film obtained from the composition for a solder photoresist ink of the present invention has adhesiveness, pencil hardness, soldering heat resistance,
It shows excellent or good performance in all of water-soluble flux properties and electrical insulation properties. On the other hand, the composition for the solder photoresist ink of Comparative Example 1 using an ultraviolet curable resin produced using only succinic anhydride having a molecular weight of 100 has poor dilute alkali developability after three days of preliminary drying. It is inferior in solder heat resistance, water-soluble flux resistance and electric insulation. The composition for a solder photoresist ink of Comparative Example 2 using an ultraviolet curable resin produced using only tetrahydrophthalic anhydride having a molecular weight of 152 is inferior in dilute alkali developability.
The composition for a solder photoresist ink of Comparative Example 3 using a mixture of an ultraviolet-curable resin manufactured using only succinic anhydride and an ultraviolet-curable resin manufactured using only tetrahydrophthalic anhydride was obtained using an ultraviolet-curable resin. Despite the fact that the ratio of the amount of succinic anhydride to the amount of tetrahydrophthalic anhydride in the resin is within the scope of the present invention, they are not reacted at the same time. , Solder heat resistance, water-soluble flux resistance,
Poor electrical insulation.
【００２１】[0021]
【発明の効果】本発明に用いる紫外線硬化性樹脂は長期
間のシェルフライフを有し、本発明のソルダーフォトレ
ジストインキ用組成物は良好な希アルカリ現像性を備え
る。また、本発明のソルダーフォトレジストインキ用組
成物の硬化塗膜は、密着性、耐熱性、耐湿性、電気絶縁
性に優れる。さらに、本発明のソルダーフォトレジスト
インキ用組成物は、プリント配線基板に塗布し仮乾燥の
後、長時間にわたって良好な希アルカリ現像性を保持
し、プリント配線基板の製造工程における仮乾燥後の作
業の中断を可能とするので、休日を挟んだプリント配線
基板の製造における生産効率を大きく向上させる効果を
有する。The ultraviolet-curable resin used in the present invention has a long shelf life, and the composition for a solder photoresist ink of the present invention has good dilute alkali developability. Further, the cured coating film of the composition for a solder photoresist ink of the present invention is excellent in adhesion, heat resistance, moisture resistance, and electrical insulation. Furthermore, after the composition for solder photoresist ink of the present invention is applied to a printed wiring board and temporarily dried, it maintains good diluted alkali developability for a long time, and the work after temporary drying in the manufacturing process of the printed wiring board. Can be interrupted, so that there is an effect that the production efficiency in the production of the printed wiring board on holidays is greatly improved.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｇ０３Ｆ 7/032 ５０１ Ｇ０３Ｆ 7/032 ５０１ 7/035 7/035 Ｈ０５Ｋ 3/28 Ｈ０５Ｋ 3/28 Ｄ (56)参考文献 特開 平７−70289（ＪＰ，Ａ) 特開 平３−253093（ＪＰ，Ａ) 特開 平４−165357（ＪＰ，Ａ) 特開 平２−173747（ＪＰ，Ａ) 特開 平６−166843（ＪＰ，Ａ) 特開 平２−308163（ＪＰ，Ａ) 特開 平６−258831（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) G03F 7/027 C08F 2/48 C09D 11/00 C09D 11/10 G03F 7/028 G03F 7/032 G03F 7/035 H05K 3/28 ────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 6 Identification code FI G03F 7/032 501 G03F 7/032 501 7/035 7/035 H05K 3/28 H05K 3/28 D (56) References JP JP-A-7-70289 (JP, A) JP-A-3-253093 (JP, A) JP-A-4-165357 (JP, A) JP-A-2-173747 (JP, A) JP-A-6-166843 (JP JP-A-2-308163 (JP, A) JP-A-6-258831 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) G03F 7/027 C08F 2/48 C09D 11/00 C09D 11/10 G03F 7/028 G03F 7/032 G03F 7/035 H05K 3/28
Claims (8)
及び熱硬化性樹脂を含有するソルダーフォトレジストイ
ンキ用組成物において、紫外線硬化性樹脂が、ノボラッ
ク型エポキシ化合物と不飽和モノカルボン酸との反応生
成物に、分子量が１２０以下の二塩基酸無水物及び分子
量が１４０以上の二塩基酸無水物をモル比が１／９〜９
／１となる割合で、同時に反応することにより得られる
ものであることを特徴とするソルダーフォトレジストイ
ンキ用組成物。1. A composition for a solder photoresist ink containing an ultraviolet-curable resin, a photopolymerization initiator, a diluent and a thermosetting resin, wherein the ultraviolet-curable resin comprises a novolak-type epoxy compound and an unsaturated monocarboxylic acid. With a dibasic acid anhydride having a molecular weight of 120 or less and a dibasic acid anhydride having a molecular weight of 140 or more in a molar ratio of 1/9 to 9
/ 1. A composition for a solder photoresist ink, which is obtained by simultaneously reacting at a ratio of / 1.
核の核数が、平均４核以上８核以下である請求項１記載
のソルダーフォトレジストインキ用組成物。2. The composition for a solder photoresist ink according to claim 1, wherein the number of phenol nuclei of the novolak type epoxy compound is from 4 to 8 on average.
に対し、当量の不飽和モノカルボン酸を反応させるもの
である請求項１〜２記載のソルダーフォトレジストイン
キ用組成物。3. The composition for a solder photoresist ink according to claim 1, wherein the epoxy group of the novolak type epoxy compound is reacted with an equivalent amount of an unsaturated monocarboxylic acid.
シ化合物と不飽和モノカルボン酸との反応生成物の有す
る水酸基１モル当たり、０.３〜１.０モルの二塩基酸無
水物を反応させたものである請求項１〜３記載のソルダ
ーフォトレジストインキ用組成物。4. The ultraviolet curable resin is reacted with 0.3 to 1.0 mol of dibasic acid anhydride per 1 mol of hydroxyl group of a reaction product of a novolak type epoxy compound and an unsaturated monocarboxylic acid. The composition for a solder photoresist ink according to claim 1, wherein
／ｇの酸価を有するものである請求項１〜４記載のソル
ダーフォトレジストインキ用組成物。5. An ultraviolet curable resin comprising 40 to 100 mg KOH.
The composition for a solder photoresist ink according to any one of claims 1 to 4, wherein the composition has an acid value of / g.
脂１００重量部当たり０.２〜２０.０重量部である請求
項１〜５記載のソルダーフォトレジストインキ用組成
物。6. The composition according to claim 1, wherein the amount of the photopolymerization initiator is 0.2 to 20.0 parts by weight per 100 parts by weight of the ultraviolet curable resin.
の中から選ばれた少なくとも１種であり、かつその配合
量が、紫外線硬化性樹脂１００重量部当たり３０〜２０
０重量部である請求項１〜６記載のソルダーフォトレジ
ストインキ用組成物。7. The diluent is at least one selected from an organic solvent and a photopolymerizable monomer, and the amount of the diluent is 30 to 20 per 100 parts by weight of the ultraviolet curable resin.
The composition for a solder photoresist ink according to claim 1, which is 0 parts by weight.
を有する重合性化合物であり、かつその配合量が紫外線
硬化性樹脂１００重量部当たり５〜６０重量部である請
求項１〜７記載のソルダーフォトレジストインキ用組成
物。8. The thermosetting resin is a polymerizable compound having at least two functional groups, and its compounding amount is 5 to 60 parts by weight per 100 parts by weight of the ultraviolet curable resin. A composition for a solder photoresist ink according to the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9600195A JP2937800B2 (en) | 1995-03-29 | 1995-03-29 | Composition for solder photoresist ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9600195A JP2937800B2 (en) | 1995-03-29 | 1995-03-29 | Composition for solder photoresist ink |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08272095A JPH08272095A (en) | 1996-10-18 |
| JP2937800B2 true JP2937800B2 (en) | 1999-08-23 |
Family
ID=14152882
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9600195A Expired - Lifetime JP2937800B2 (en) | 1995-03-29 | 1995-03-29 | Composition for solder photoresist ink |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2937800B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY121423A (en) * | 1998-06-26 | 2006-01-28 | Ciba Sc Holding Ag | Photopolymerizable thermosetting resin compositions |
| SG78412A1 (en) | 1999-03-31 | 2001-02-20 | Ciba Sc Holding Ag | Oxime derivatives and the use thereof as latent acids |
| JP2001081416A (en) * | 1999-09-13 | 2001-03-27 | Nippon Steel Chem Co Ltd | Cured film and color filter prepared by using same |
| SG97168A1 (en) | 1999-12-15 | 2003-07-18 | Ciba Sc Holding Ag | Photosensitive resin composition |
| JP2002107926A (en) * | 2000-09-29 | 2002-04-10 | Taiyo Ink Mfg Ltd | Photosensitive resin composition |
| CN102781911B (en) | 2010-02-24 | 2015-07-22 | 巴斯夫欧洲公司 | Latent acids and their use |
| JP2015152854A (en) * | 2014-02-18 | 2015-08-24 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition, photosensitive resin laminate, and resist pattern forming method |
| JP6482213B2 (en) * | 2014-09-05 | 2019-03-13 | 住友ゴム工業株式会社 | Sample preparation method and sample observation method |
| KR102537349B1 (en) | 2015-02-02 | 2023-05-26 | 바스프 에스이 | Potential Acids and Their Uses |
-
1995
- 1995-03-29 JP JP9600195A patent/JP2937800B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08272095A (en) | 1996-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101009081B1 (en) | Photocurable and thermosetting resin compositions and printed wiring boards using the same | |
| JP6204734B2 (en) | Resin composition for solder resist | |
| JP3405631B2 (en) | Epoxy resin composition, photo solder resist ink, printed wiring board, and method of manufacturing the same | |
| JP5027458B2 (en) | Photo-curable and thermosetting one-component solder resist composition and printed wiring board using the same | |
| JP4655362B2 (en) | Method for producing photosensitive resin | |
| JP2008019336A (en) | Photo-curable and thermosetting one-component solder resist composition and printed wiring board using the same | |
| JP2937800B2 (en) | Composition for solder photoresist ink | |
| JPH01161038A (en) | Resin composition and solder resist resin composition | |
| JP2981218B1 (en) | Solder photoresist ink composition | |
| JPH08335768A (en) | Alkaline developable one liquid photosolder resist composition and solder resist film obtainable from the resist | |
| KR20060081361A (en) | Photocurable and thermosetting one-component solder resist compositions and printed wiring boards using the same | |
| JP2000109541A (en) | Photosensitive and thermosetting resin composition | |
| JPS60121444A (en) | Alkali-developable photosensitive resin composition | |
| JP2802801B2 (en) | Photosensitive thermosetting resin composition and solder resist pattern forming method | |
| WO2002096969A1 (en) | Light- and heat-curing resin composition | |
| JP2963069B2 (en) | Solder photoresist ink composition | |
| JP2003280190A (en) | Photosetting and thermosetting resin composition | |
| JP2896636B2 (en) | Composition for solder photoresist ink | |
| JP2004264773A (en) | Photosensitive resin composition, its cured product and printed wiring board | |
| JP2835539B2 (en) | Photosensitive thermosetting resin composition and pattern forming method | |
| JP2884046B2 (en) | Method for producing UV-curable resin | |
| JP2003280189A (en) | Photosetting and thermosetting resin composition | |
| JPH06138655A (en) | Photosensitive thermosetting resin composition | |
| JP2001264977A (en) | Photosensitive resin composition | |
| JP2001013684A (en) | Photosensitive resin composition and its cured body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080611 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090611 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090611 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100611 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100611 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110611 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110611 Year of fee payment: 12 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120611 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120611 Year of fee payment: 13 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130611 Year of fee payment: 14 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |