JP6819104B2 - Unsaturated group-containing alkaline developable resin and resin material for solder resist - Google Patents
Unsaturated group-containing alkaline developable resin and resin material for solder resist Download PDFInfo
- Publication number
- JP6819104B2 JP6819104B2 JP2016135056A JP2016135056A JP6819104B2 JP 6819104 B2 JP6819104 B2 JP 6819104B2 JP 2016135056 A JP2016135056 A JP 2016135056A JP 2016135056 A JP2016135056 A JP 2016135056A JP 6819104 B2 JP6819104 B2 JP 6819104B2
- Authority
- JP
- Japan
- Prior art keywords
- mass
- resin
- parts
- group
- alkaline developable
- 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.)
- Active
Links
- 229920005989 resin Polymers 0.000 title claims description 88
- 239000011347 resin Substances 0.000 title claims description 88
- 239000000463 material Substances 0.000 title claims description 15
- 229910000679 solder Inorganic materials 0.000 title claims description 15
- 239000003822 epoxy resin Substances 0.000 claims description 56
- 229920000647 polyepoxide Polymers 0.000 claims description 56
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 35
- 239000000047 product Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- -1 2,7-dihydroxynaphthalene compound Chemical class 0.000 claims description 23
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 19
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 18
- 239000011342 resin composition Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 19
- 229920003986 novolac Polymers 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 238000007664 blowing Methods 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 8
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 7
- 239000005011 phenolic resin Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000011973 solid acid Substances 0.000 description 7
- 238000012719 thermal polymerization Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 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 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- 238000005259 measurement Methods 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 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 5
- 239000003513 alkali Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229940014800 succinic anhydride Drugs 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 2
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 206010034960 Photophobia Diseases 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000009477 glass transition Effects 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
- 208000013469 light sensitivity Diseases 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Chemical group 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVIQBUBNVYWIDV-UHFFFAOYSA-N 2-methoxy-2-(2-methoxyphenyl)-1-phenylethanone Chemical compound C=1C=CC=C(OC)C=1C(OC)C(=O)C1=CC=CC=C1 SVIQBUBNVYWIDV-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 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 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Images
Landscapes
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、現像性及び硬化物における耐熱性に優れる不飽和基含有アルカリ現像性樹脂、これを含有する光硬化型アルカリ現像性樹脂組成物とその硬化物、ソルダーレジスト用樹脂材料とレジスト部材に関する。 The present invention relates to an unsaturated group-containing alkaline developable resin having excellent developability and heat resistance in a cured product, a photocurable alkaline developable resin composition containing the same, a cured product thereof, a resin material for solder resist, and a resist member. ..
プリント配線基板用のソルダーレジスト用樹脂材料には、エポキシ樹脂をアクリル酸でアクリレート化した後、酸無水物を反応させて得られる酸ペンダント型エポキシアクリレートが広く用いられている。ソルダーレジスト用樹脂材料に対する要求性能は、少ない露光量で硬化すること、アルカリ現像性に優れること、硬化物における耐熱性が高いこと、基材密着性に優れること、誘電特性に優れるなど様々なものが挙げられる。中でも、現像性と耐熱性とは基本的かつ重要な性能であり、両性能のバランスに優れ、プリント配線基板の製造効率及び製造作業性の向上と、最終製品の品質信頼性向上を実現できる樹脂材料の開発が求められている。 As a resin material for solder resist for a printed wiring board, an acid pendant type epoxy acrylate obtained by reacting an epoxy resin with acrylic acid and then reacting with an acid anhydride is widely used. There are various required performances for resin materials for solder resist, such as curing with a small exposure amount, excellent alkali developability, high heat resistance in cured products, excellent substrate adhesion, and excellent dielectric properties. Can be mentioned. Among them, developability and heat resistance are basic and important performances, and a resin that has an excellent balance between both performances, can improve the manufacturing efficiency and workability of printed wiring boards, and improve the quality reliability of final products. The development of materials is required.
従来知られているソルダーレジスト用樹脂材料として、クレゾールノボラック型エポキシ樹脂とアクリル酸と無水メタクリル酸とを反応させて得られる中間体に、更にテトラヒドロ無水フタル酸を反応させて得られる酸ペンダント型エポキシアクリレートが知られているが（下記特許文献１参照）、特に耐熱性が十分ではなく、昨今ますます高まる要求性能を満足するものではなかった。 As a conventionally known resin material for solder resist, an acid pendant type epoxy obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a cresol novolac type epoxy resin with acrylic acid and methacrylic anhydride. Although acrylate is known (see Patent Document 1 below), its heat resistance is not sufficient, and it does not satisfy the increasingly required performance these days.
したがって、本発明が解決しようとする課題は、現像性及び硬化物における耐熱性に優れる不飽和基含有アルカリ現像性樹脂、これを含有する光硬化型アルカリ現像性脂組成物とその硬化物、ソルダーレジスト用樹脂材料とレジスト部材を提供することにある。 Therefore, the problem to be solved by the present invention is an unsaturated group-containing alkaline developable resin having excellent developability and heat resistance in a cured product, a photocurable alkaline developable fat composition containing the same, a cured product thereof, and a solder. It is an object of the present invention to provide a resin material for resist and a resist member.
本発明者らは、上記課題を解決するため鋭意検討を行った結果、２，７−ジヒドロキシナフタレン化合物とホルムアルデヒドとの特定条件下での反応物をポリグリシジルエーテル化して得られるエポキシ樹脂を原料とする酸ペンダント型エポキシアクリレートが、現像性及び硬化物における耐熱性に優れることを見出し、本発明を完成させるに至った。 As a result of diligent studies to solve the above problems, the present inventors used an epoxy resin obtained by polyglycidyl etherification of a reaction product of a 2,7-dihydroxynaphthalene compound and formaldehyde under specific conditions as a raw material. We have found that the acid pendant type epoxy acrylate is excellent in developability and heat resistance in a cured product, and have completed the present invention.
即ち、本発明は、下記構造式（１） That is, the present invention has the following structural formula (1).
の何れかで表される構造部位である。式中Ｒ１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子の何れかであり、ｎは１〜４の整数、ｍは１〜５の整数である。］
で表される分子構造を有する化合物（α）を含有し、樹脂中に存在するＸのうち少なくとも一つが前記構造式（２−１）で表される構造部位であり、少なくとも一つが前記構造式（２−２）で表される構造部位であることを特徴とする不飽和基含有アルカリ現像性樹脂に関する。
It is a structural part represented by any of. In the formula, R 1 is independently any of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom, n is an integer of 1 to 4, and m is an integer of 1 to 5. ]
It contains a compound (α) having a molecular structure represented by, and at least one of X present in the resin is a structural site represented by the structural formula (2-1), and at least one is the structural formula. The present invention relates to an unsaturated group-containing alkaline developable resin characterized by being a structural portion represented by (2-2).
本発明はさらに、前記不飽和基含有アルカリ現像性樹脂と、光重合開始剤とを含有する光硬化型アルカリ現像性樹脂組成物に関する。 The present invention further relates to a photocurable alkaline developable resin composition containing the unsaturated group-containing alkaline developable resin and a photopolymerization initiator.
本発明はさらに、前記光硬化型アルカリ現像性樹脂組成物を硬化させてなる硬化物に関する。 The present invention further relates to a cured product obtained by curing the photocurable alkaline developable resin composition.
本発明はさらに、前記不飽和基含有アルカリ現像性樹脂と、光重合開始剤とを含有するソルダーレジスト用樹脂材料に関する。 The present invention further relates to a resin material for a solder resist containing the unsaturated group-containing alkaline developable resin and a photopolymerization initiator.
本発明はさらに、前記ソルダーレジスト用樹脂材料を用いてなるレジスト部材に関する。 The present invention further relates to a resist member made of the above resin material for solder resist.
本発明はさらに、２，７−ジヒドロキシナフタレン化合物とホルムアルデヒドとを、２，７−ジヒドロキシナフタレン化合物１モルに対し０．２〜２．０モルのアルカリ触媒の存在下で反応させ、得られた反応生成物とエピハロヒドリンとを反応させて得られるエポキシ樹脂（ａ１）、不飽和モノカルボン酸（ａ２）、不飽和モノカルボン酸無水物（ａ３）、及びジカルボン酸無水物（ａ４）を必須の原料として反応させる不飽和基含有アルカリ現像性樹脂の製造方法に関する。 The present invention further reacts a 2,7-dihydroxynaphthalene compound with formaldehyde with 1 mol of the 2,7-dihydroxynaphthalene compound in the presence of 0.2 to 2.0 mol of an alkali catalyst to obtain the reaction. Epoxy resin (a1), unsaturated monocarboxylic acid (a2), unsaturated monocarboxylic acid anhydride (a3), and dicarboxylic acid anhydride (a4) obtained by reacting the product with epihalohydrin are essential raw materials. The present invention relates to a method for producing an alkali-developable resin containing an unsaturated group to be reacted.
本発明によれば、現像性及び硬化物における耐熱性に優れる不飽和基含有アルカリ現像性樹脂、これを含有する光硬化型アルカリ現像性樹脂組成物とその硬化物、ソルダーレジスト用樹脂材料とレジスト部材を提供することができる。 According to the present invention, an unsaturated group-containing alkaline developable resin having excellent developability and heat resistance in a cured product, a photocurable alkaline developable resin composition containing the same, a cured product thereof, a resin material for solder resist and a resist. Members can be provided.
以下、本発明を詳細に説明する。
本発明の不飽和基含有アルカリ現像性樹脂は、下記構造式（１）
Hereinafter, the present invention will be described in detail.
The unsaturated group-containing alkaline developable resin of the present invention has the following structural formula (1).
の何れかで表される構造部位である。式中Ｒ１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子の何れかであり、ｎは１〜４の整数、ｍは１〜５の整数である。］
で表される分子構造を有する化合物（α）を含有し、樹脂中に存在するＸのうち少なくとも一つが前記構造式（２−１）で表される構造部位であり、少なくとも一つが前記構造式（２−２）で表される構造部位であることを特徴とする。
It is a structural part represented by any of. In the formula, R 1 is independently any of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom, n is an integer of 1 to 4, and m is an integer of 1 to 5. ]
It contains a compound (α) having a molecular structure represented by, and at least one of X existing in the resin is a structural site represented by the structural formula (2-1), and at least one is the structural formula. It is characterized by being a structural part represented by (2-2).
式中Ｒ１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子の何れかである。前記アルキル基は、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、へキシル基、シクロへキシル基等が挙げられる。前記アルコキシ基は、例えば、メトキシ基、エトキシ基、プロピルオキシ基、ブトキシ基、ペンチルオキシ基、へキシルオキシ基、シクロへキシルオキシ基等が挙げられる。前記ハロゲン原子はフッ素原子、塩素原子、臭素原子が挙げられる。中でも、耐熱性に優れる不飽和基含有アルカリ現像性樹脂となることから、Ｒ１は水素原子であることが好ましい。 In the formula, R 1 is independently any of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a cyclohexyloxy group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Among them, R 1 is preferably a hydrogen atom because it is an unsaturated group-containing alkaline developable resin having excellent heat resistance.
前記Ｒ３は炭素原子数１〜１０の炭化水素基であり、その具体構造は特に限定されず、直鎖のアルキレン基、分岐構造を有するアルキレン基、二重結合を有するもの、三重結合を有するもの、脂環構造を有するもの、芳香環構造を有するもの、いずれの構造でも良い。具体的には、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、へキシレン基、シクロへキシレン基、テトラヒドロフェニレン基、キシリレン基等が挙げられる。 The R 3 is a hydrocarbon group having 1 to 10 carbon atoms, and its specific structure is not particularly limited, and has a linear alkylene group, an alkylene group having a branched structure, a double bond, and a triple bond. , A structure having an alicyclic structure, and a structure having an aromatic ring structure may be used. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclohexylene group, a tetrahydrophenylene group, and a xylene group.
前記化合物（α）を含有する本発明の不飽和基含有アルカリ現像性樹脂を製造する方法は特に限定されないが、例えば、２，７−ジヒドロキシナフタレン化合物とホルムアルデヒドとを、２，７−ジヒドロキシナフタレン化合物１モルに対し０．２〜２．０モルのアルカリ触媒の存在下で反応させ、得られた反応生成物とエピハロヒドリンとを反応させて得られるエポキシ樹脂（ａ１）、（メタ）アクリル酸（ａ２）、（メタ）アクリル酸無水物（ａ３）、及びジカルボン酸無水物（ａ４）を必須の原料として反応させる方法により得ることができる。 The method for producing the unsaturated group-containing alkali-developable resin of the present invention containing the compound (α) is not particularly limited. For example, a 2,7-dihydroxynaphthalene compound and a formaldehyde are used as a 2,7-dihydroxynaphthalene compound. Epoxy resin (a1) and (meth) acrylic acid (a2) obtained by reacting 1 mol with an alkaline catalyst of 0.2 to 2.0 mol and reacting the obtained reaction product with epihalohydrin. ), (Meta) acrylic anhydride (a3), and dicarboxylic acid anhydride (a4) can be obtained by a reaction method as an essential raw material.
前記製造方法につき詳述するに、まず、２，７−ジヒドロキシナフタレン化合物とホルムアルデヒドとを、２，７−ジヒドロキシナフタレン化合物１モルに対し０．２〜２．０モルのアルカリ触媒の存在下で反応させて、下記構造式（３） To describe the production method in detail, first, the 2,7-dihydroxynaphthalene compound and formaldehyde are reacted with 1 mol of the 2,7-dihydroxynaphthalene compound in the presence of 0.2 to 2.0 mol of an alkaline catalyst. Then, the following structural formula (3)
で表される分子構造を有する化合物（α’）を含有するフェノール樹脂中間体を得る。
A phenol resin intermediate containing a compound (α') having a molecular structure represented by is obtained.
前記２，７−ジヒドロキシナフタレン化合物は、２，７−ジヒドロキシナフタレンや２，７−ジヒドロキシナフタレンの芳香核上にアルキル基、アルコキシ基、ハロゲン原子等の置換基を一つ乃至複数有する各種の化合物が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。中でも、耐熱性に優れる不飽和基含有アルカリ現像性樹脂が得られることから、２，７−ジヒドロキシナフタレンが好ましい。 The 2,7-dihydroxynaphthalene compound includes various compounds having one or more substituents such as an alkyl group, an alkoxy group, and a halogen atom on the aromatic nuclei of 2,7-dihydroxynaphthalene and 2,7-dihydroxynaphthalene. Can be mentioned. Each of these may be used alone, or two or more types may be used in combination. Of these, 2,7-dihydroxynaphthalene is preferable because an unsaturated group-containing alkaline developable resin having excellent heat resistance can be obtained.
ホルムアルデヒドは何れの形態のものを用いても良く、水溶液の状態であるホルマリン溶液でも、固形状態であるパラホルムアルデヒドでも良い。ホルムアルデヒドの仕込み量は特に限定されないが、２，７−ジヒドロキシナフタレン化合物１モルに対してホルムアルデヒドが０．６〜２．０モルの範囲となる割合であることが好ましく、０．６〜１．５モルの範囲となる割合であることがより好ましい。 Formaldehyde may be in any form, and may be a formalin solution in an aqueous solution state or paraformaldehyde in a solid state. The amount of formaldehyde charged is not particularly limited, but the ratio of formaldehyde to 1 mol of the 2,7-dihydroxynaphthalene compound is preferably in the range of 0.6 to 2.0 mol, preferably 0.6 to 1.5 mol. More preferably, the ratio is in the range of moles.
前記アルカリ触媒は、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、金属ナトリウム、金属リチウム等のアルカリ金属、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。 Examples of the alkali catalyst include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metals such as sodium metal and lithium metal, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Each of these may be used alone, or two or more types may be used in combination.
２，７−ジヒドロキシナフタレン化合物とホルムアルデヒドとの反応は、例えば、２０〜１５０℃程度の温度条件下、１〜１０時間程度反応させる方法により行うことができる。該反応は必要に応じて有機溶剤中で行っても良い。有機溶剤の選択は、２，７−ジヒドロキシナフタレン化合物、ホルムアルデヒド、及び生成物である前記化合物（α’）の溶解性や、反応温度条件により適宜選択されるが、例えば、メチルセロソルブ、イソプロピルアルコール、エチルセロソルブ、トルエン、キシレン、メチルイソブチルケトン等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上の混合溶媒としても良い。有機溶剤の使用量は、反応効率が良好となることから、２，７−ジヒドロキシナフタレン化合物及びホルムアルデヒドの合計質量に対し０．１〜５倍量程度の範囲で用いることが好ましい。 The reaction between the 2,7-dihydroxynaphthalene compound and formaldehyde can be carried out, for example, by a method of reacting for about 1 to 10 hours under a temperature condition of about 20 to 150 ° C. The reaction may be carried out in an organic solvent if necessary. The organic solvent is appropriately selected depending on the solubility of the 2,7-dihydroxynaphthalene compound, formaldehyde, and the compound (α') which is a product, and the reaction temperature conditions. For example, methyl cellosolve, isopropyl alcohol, etc. Examples thereof include ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. Each of these may be used alone or as a mixed solvent of two or more kinds. The amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the 2,7-dihydroxynaphthalene compound and formaldehyde because the reaction efficiency is good.
２，７−ジヒドロキシナフタレン化合物とホルムアルデヒドとの反応終了後は、中和或いは水洗処理を行い、前記化合物（α’）を含有するフェノール樹脂中間体を得る。必要に応じて精密濾過等の精製処理を行っても良い。 After completion of the reaction between the 2,7-dihydroxynaphthalene compound and formaldehyde, neutralization or washing with water is performed to obtain a phenol resin intermediate containing the compound (α'). If necessary, purification treatment such as microfiltration may be performed.
続くフェノール樹脂中間体とエピハロヒドリンとの反応は公知慣用の方法にて行うことができ、具体的には、水酸化ナトリウム、水酸化カリウム等のアルカリ触媒の存在下、２０〜１２０℃程度の温度条件で０．５〜１０時間反応させる方法が挙げられる。前記アルカリ触媒の添加量は、前記フェノール樹脂中間体中のフェノール性水酸基１モルに対し０．９〜２．０モルの範囲であることが好ましい。また、エピハロヒドリンの仕込み量は、前記フェノール樹脂中間体中のフェノール性水酸基１モルに対し、２〜１０モルの範囲であることが好ましい。該反応は必要に応じて有機溶剤中で行っても良い。反応終了後は、反応生成物を水洗後、加熱減圧条件下で未反応のエピハロヒドリンや有機溶剤等を除去し、前記エポキシ樹脂（ａ１）を得る。エポキシ樹脂（ａ１）のエポキシ当量は、１５０〜３００ｇ/当量の範囲であることが好ましい。 The subsequent reaction between the phenolic resin intermediate and epihalohydrin can be carried out by a known and commonly used method. Specifically, in the presence of an alkaline catalyst such as sodium hydroxide or potassium hydroxide, the temperature condition is about 20 to 120 ° C. A method of reacting with 0.5 to 10 hours can be mentioned. The amount of the alkali catalyst added is preferably in the range of 0.9 to 2.0 mol with respect to 1 mol of the phenolic hydroxyl group in the phenol resin intermediate. The amount of epihalohydrin charged is preferably in the range of 2 to 10 mol with respect to 1 mol of the phenolic hydroxyl group in the phenol resin intermediate. The reaction may be carried out in an organic solvent if necessary. After completion of the reaction, the reaction product is washed with water and then unreacted epihalohydrin, an organic solvent and the like are removed under heating and reduced pressure conditions to obtain the epoxy resin (a1). The epoxy equivalent of the epoxy resin (a1) is preferably in the range of 150 to 300 g / equivalent.
前記エポキシ樹脂（ａ１）、（メタ）アクリル酸（ａ２）、（メタ）アクリル酸無水物（ａ３）及びジカルボン酸無水物（ａ４）を必須の原料として反応させる方法は特に限定されず、例えば、これら全てを一括で反応させる方法でも、順次反応させる方法でも、どちらでも良い。中でも、反応の制御が容易であることから、まず前記エポキシ樹脂（ａ１）、（メタ）アクリル酸（ａ２）、（メタ）アクリル酸無水物（ａ３）を反応させ、次いで、前記ジカルボン酸無水物（ａ４）を反応させる方法が好ましい。該反応は、例えば、前記エポキシ樹脂（ａ１）、（メタ）アクリル酸（ａ２）、及び（メタ）アクリル酸無水物（ａ３）を、有機溶媒中、エステル化反応触媒と、酸化防止剤、重合禁止剤との存在下で、１００〜１５０℃の温度範囲で５〜１２時間程度反応させた後、反応系中にジカルボン酸無水物（ａ４）を加え、９０〜１２０℃の温度範囲で１〜５時間程度反応させる方法により行うことができる。 The method for reacting the epoxy resin (a1), (meth) acrylic acid (a2), (meth) acrylic anhydride (a3) and dicarboxylic acid anhydride (a4) as essential raw materials is not particularly limited, and for example, Either a method of reacting all of them all at once or a method of reacting them sequentially may be used. Above all, since the reaction is easy to control, the epoxy resin (a1), (meth) acrylic acid (a2), and (meth) acrylic anhydride (a3) are first reacted, and then the dicarboxylic acid anhydride is reacted. The method of reacting (a4) is preferable. In the reaction, for example, the epoxy resin (a1), (meth) acrylic acid (a2), and (meth) acrylic anhydride (a3) are polymerized with an esterification reaction catalyst in an organic solvent, an antioxidant, and the like. After reacting in the presence of a banning agent in a temperature range of 100 to 150 ° C. for about 5 to 12 hours, dicarboxylic acid anhydride (a4) is added to the reaction system, and 1 to 1 in a temperature range of 90 to 120 ° C. It can be carried out by a method of reacting for about 5 hours.
前記エポキシ樹脂（ａ１）、（メタ）アクリル酸（ａ２）、及び（メタ）アクリル酸無水物（ａ３）の反応割合は、エポキシ樹脂（ａ１）中のエポキシ基１モルに対し、（メタ）アクリル酸（ａ２）と（メタ）アクリル酸無水物（ａ３）とを合計で０．９〜１．１モルの範囲で用いることが好ましい。 The reaction ratio of the epoxy resin (a1), (meth) acrylic acid (a2), and (meth) acrylic anhydride (a3) was (meth) acrylic with respect to 1 mol of the epoxy group in the epoxy resin (a1). It is preferable to use the acid (a2) and the (meth) acrylic anhydride (a3) in a total range of 0.9 to 1.1 mol.
また、得られる不飽和基含有アルカリ現像性樹脂の現像性と、硬化物における耐熱性及び誘電特性とのバランスに優れることから、（メタ）アクリル酸（ａ２）と（メタ）アクリル酸無水物（ａ３）とのモル比［（ａ２）/（ａ３）］の値が、０．３〜２．０の範囲であることがより好ましい。 Further, since the obtained unsaturated group-containing alkaline developable resin has an excellent balance between the developability and the heat resistance and dielectric properties of the cured product, (meth) acrylic acid (a2) and (meth) acrylic anhydride (meth) acrylic anhydride (meth) It is more preferable that the value of the molar ratio [(a2) / (a3)] with a3) is in the range of 0.3 to 2.0.
前記有機溶剤の選択は、各原料及び生成物である化合物（α）の溶解性や、反応温度条件により適宜選択されるが、例えば、メチルエチルケトン、アセトン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、エチルジグリコールアセテート等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上の混合溶媒としても良い。有機溶剤の使用量は、反応効率が良好となることから、前記エポキシ樹脂（ａ１）、（メタ）アクリル酸（ａ２）、（メタ）アクリル酸無水物（ａ３）及びジカルボン酸無水物（ａ４）の合計質量に対し０．１〜５倍量程度の範囲で用いることが好ましい。 The selection of the organic solvent is appropriately selected depending on the solubility of each raw material and the product compound (α) and the reaction temperature conditions. For example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone. , Methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl diglycol acetate and the like. Each of these may be used alone or as a mixed solvent of two or more kinds. The amount of the organic solvent used is such that the reaction efficiency is good, so that the epoxy resin (a1), (meth) acrylic acid (a2), (meth) acrylic anhydride (a3) and dicarboxylic acid anhydride (a4) are used. It is preferable to use the amount in the range of about 0.1 to 5 times the total mass of.
前記エステル化反応触媒は、例えば、トリメチルホスフィン、トリブチルホスフィン、トリフェニルホスフィン等のリン化合物、トリエチルアミン、トリブチルアミン、ジメチルベンジルアミン等のアミン化合物等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。触媒の添加量は、前記エポキシ樹脂（ａ１）、（メタ）アクリル酸（ａ２）、（メタ）アクリル酸無水物（ａ３）及びジカルボン酸無水物（ａ４）の合計質量に対し０．０５〜５質量％の範囲で用いることが好ましい。 Examples of the esterification reaction catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, and amine compounds such as triethylamine, tributylamine and dimethylbenzylamine. Each of these may be used alone, or two or more types may be used in combination. The amount of the catalyst added is 0.05 to 5 with respect to the total mass of the epoxy resin (a1), (meth) acrylic acid (a2), (meth) acrylic anhydride (a3) and dicarboxylic acid anhydride (a4). It is preferably used in the range of mass%.
前記ジカルボン酸無水物（ａ４）は、一分子中に二つのカルボキシ基を有する化合物の酸無水物であれば、いずれのものも利用できる。具体的にはシュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸等のジカルボン酸化合物の酸無水物が挙げられる。ジカルボン酸無水物（Ｄ）はそれぞれ単独で用いても良いし、２種類以上を併用しても良い。中でも、硬化物における耐熱性に優れる（メタ）アクリレート樹脂となる点では、フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸等、分子構造中に環状構造を有する化合物の酸無水物が好ましい。また、現像性に優れる（メタ）アクリレート樹脂となる点では、コハク酸無水物が好ましい。 As the dicarboxylic acid anhydride (a4), any acid anhydride of a compound having two carboxy groups in one molecule can be used. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, Examples thereof include acid anhydrides of dicarboxylic acid compounds such as hexahydrophthalic acid and methylhexahydrophthalic acid. The dicarboxylic acid anhydride (D) may be used alone or in combination of two or more. Among them, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, etc. have a cyclic structure in the molecular structure in that they become (meth) acrylate resins having excellent heat resistance in cured products. The acid anhydride of the compound having is preferable. Further, succinic anhydride is preferable in that it becomes a (meth) acrylate resin having excellent developability.
前記ジカルボン酸無水物（ａ４）の反応割合は、前記（メタ）アクリル酸（ａ２）１モルに対し、０．９〜１．１モルの範囲で用いることが好ましい。 The reaction ratio of the dicarboxylic acid anhydride (a4) is preferably in the range of 0.9 to 1.1 mol with respect to 1 mol of the (meth) acrylic acid (a2).
このようにして得られる不飽和基含有アルカリ現像性樹脂は、前記構造式（１）で表される分子構造を有する化合物（α）の他、下記構造式（４） The unsaturated group-containing alkaline developable resin thus obtained has the following structural formula (4) in addition to the compound (α) having the molecular structure represented by the structural formula (1).
の何れかで表される構造部位である。式中Ｒ１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子の何れかであり、ｎは１〜４の整数、ｍは１〜５の整数である。］
で表される化合物（β）や、オリゴマー成分（γ）を含有していても良い。なお、前記オリゴマー成分（γ）とは、不飽和基含有アルカリ現像性樹脂の製造工程で副生する、前記化合物（α）や（β）よりも大きい分子量を有する成分の総称であり、ジヒドロキシナフタレンノボラック構造を有するものや、エポキシの開環反応等により副生した成分、ジカルボン酸無水物（ａ４）により架橋した成分等を含む。
It is a structural part represented by any of. In the formula, R 1 is independently any of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom, n is an integer of 1 to 4, and m is an integer of 1 to 5. ]
It may contain a compound (β) represented by (β) or an oligomer component (γ). The oligomer component (γ) is a general term for components having a molecular weight larger than that of the compounds (α) and (β), which are by-produced in the manufacturing process of the unsaturated group-containing alkaline developable resin, and are dihydroxynaphthalene. It contains a component having a novolak structure, a component produced as a by-product by an epoxy ring-opening reaction, a component crosslinked with a dicarboxylic acid anhydride (a4), and the like.
不飽和基含有アルカリ現像性樹脂がこれらの成分を含有する場合の各成分の含有量は、不飽和基含有アルカリ現像性樹脂１００質量部中、前記化合物（α）を５質量部以上含有することが好ましく、５〜２０質量部の範囲で含有することがより好ましい。更に、不飽和基含有アルカリ現像性樹脂１００質量部中、前記化合物（β）を１５〜５０質量部の範囲で含有することが好ましく、前記オリゴマー成分（γ）を３０〜８０質量部の範囲で含有することが好ましい。 When the unsaturated group-containing alkaline developable resin contains these components, the content of each component shall be 5 parts by mass or more of the compound (α) in 100 parts by mass of the unsaturated group-containing alkaline developable resin. Is preferable, and the content is more preferably in the range of 5 to 20 parts by mass. Further, the compound (β) is preferably contained in the range of 15 to 50 parts by mass, and the oligomer component (γ) is contained in the range of 30 to 80 parts by mass in 100 parts by mass of the unsaturated group-containing alkaline developable resin. It is preferable to contain it.
本発明の不飽和基含有アルカリ現像性樹脂の酸価は、耐熱性と現像性とのバランスに優れるものとなることから４０〜９０ｍｇＫＯＨ/ｇの範囲であることが好ましい。なお、本願発明において不飽和基含有アルカリ現像性樹脂の酸価はＪＩＳ Ｋ ００７０（１９９２）の中和滴定法にて測定される値である。 The acid value of the unsaturated group-containing alkaline developable resin of the present invention is preferably in the range of 40 to 90 mgKOH / g because it provides an excellent balance between heat resistance and developability. In the present invention, the acid value of the unsaturated group-containing alkaline developable resin is a value measured by the neutralization titration method of JIS K 0070 (1992).
本発明の不飽和基含有アルカリ現像性樹脂は、分子構造中に重合性の（メタ）アクリロイル基を有することから、例えば、光重合開始剤を添加することにより光硬化型アルカリ現像性樹脂組成物として利用することができる。 Since the unsaturated group-containing alkali-developable resin of the present invention has a polymerizable (meth) acryloyl group in the molecular structure, for example, a photocurable alkaline-developable resin composition by adding a photopolymerization initiator. Can be used as.
前記光重合開始剤は、例えば、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−〔４−（２−ヒドロキシエトキシ）フェニル〕−２−ヒドロキシ−２−メチル−１−プロパン−１−オン、チオキサントン及びチオキサントン誘導体、２，２′−ジメトキシ−１，２−ジフェニルエタン−１−オン、２，４，６−トリメチルベンゾイルジフェニルホスフィンオキシド、ビス（２，４，６−トリメチルベンゾイル）フェニルホスフィンオキシド、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−１−プロパノン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタン−１−オン等が挙げられる。 The photopolymerization initiator is, for example, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy. -2-Methyl-1-propan-1-one, thioxanthone and thioxanthone derivative, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphenyl oxide, bis ( 2,4,6-trimethylbenzoyl) phenylphosphenyl oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-) Examples thereof include morpholinophenyl) -butane-1-one.
これら光重合開始剤の市販品は、例えば、「イルガキュア−１８４」、「イルガキュア−１４９」、「イルガキュア−２６１」、「イルガキュア−３６９」、「イルガキュア−５００」、「イルガキュア−６５１」、「イルガキュア−７５４」、「イルガキュア−７８４」、「イルガキュア−８１９」、「イルガキュア−９０７」、「イルガキュア−１１１６」、「イルガキュア−１６６４」、「イルガキュア−１７００」、「イルガキュア−１８００」、「イルガキュア−１８５０」、「イルガキュア−２９５９」、「イルガキュア−４０４３」、「ダロキュア−１１７３」（チバスペシャルティーケミカルズ社製）、「ルシリンＴＰＯ」（ビーエーエスエフ社製）、「カヤキュア−ＤＥＴＸ」、「カヤキュア−ＭＢＰ」、「カヤキュア−ＤＭＢＩ」、「カヤキュア−ＥＰＡ」、「カヤキュア−ＯＡ」（日本化薬株式会社製）、「バイキュア−１０」、「バイキュア−５５」（ストウファ・ケミカル社製）、「トリゴナルＰ１」（アクゾ社製）、「サンドレイ１０００」（サンドズ社製）、「ディープ」（アプジョン社製）、「クオンタキュア−ＰＤＯ」、「クオンタキュア−ＩＴＸ」、「クオンタキュア−ＥＰＤ」（ワードブレンキンソップ社製）等が挙げられる。 Commercially available products of these photopolymerization initiators include, for example, "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500", "Irgacure-651", and "Irgacure". -754 "," Irgacure-784 "," Irgacure-819 "," Irgacure-907 "," Irgacure-1116 "," Irgacure-1664 "," Irgacure-1700 "," Irgacure-1800 "," Irgacure-1850 " , "Irgacure-2959", "Irgacure-4043", "DaroCure-1173" (manufactured by Ciba Specialty Chemicals), "Lucillin TPO" (manufactured by BASF), "Kayacure-DETX", "Kayacure-MBP" , "Kayacure-DMBI", "Kayacure-EPA", "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "BiCure-10", "BiCure-55" (manufactured by Stofa Chemical Co., Ltd.), "Trigonal P1" (Akzo), "Sandray 1000" (Sands), "Deep" (Apjon), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (Word Brenkinsop) (Manufactured by the company) and the like.
前記光重合開始剤の添加量は、例えば、光硬化型アルカリ現像性樹脂組成物１００質量部に対し、１〜２０質量部の範囲で用いる。 The amount of the photopolymerization initiator added is, for example, in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the photocurable alkaline developable resin composition.
本発明の光硬化型アルカリ現像性樹脂組成物は、前記本発明の不飽和基含有アルカリ現像性樹脂以外の樹脂成分を含有しても良い。該樹脂成分は、例えば、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂等のエポキシ樹脂に、（メタ）アクリル酸、ジカルボン酸無水物、必要に応じて不飽和モノカルボン酸無水物等を反応させて得られるような、樹脂中にカルボキシル基と（メタ）アクリロイル基とを有する樹脂、各種の（メタ）アクリレートモノマー等が挙げられる。 The photocurable alkali-developable resin composition of the present invention may contain a resin component other than the unsaturated group-containing alkali-developable resin of the present invention. The resin component is obtained by reacting an epoxy resin such as a bisphenol type epoxy resin or a novolak type epoxy resin with (meth) acrylic acid, a dicarboxylic acid anhydride, or an unsaturated monocarboxylic acid anhydride if necessary. Examples thereof include resins having a carboxyl group and a (meth) acryloyl group in the resin, various (meth) acrylate monomers, and the like.
本発明の光硬化型アルカリ現像性樹脂組成物は、この他、無機微粒子やポリマー微粒子、顔料、消泡剤、粘度調整剤、レベリング剤、難燃剤、保存安定化剤等の各種添加剤を含有しても良い。 The photocurable alkaline developable resin composition of the present invention also contains various additives such as inorganic fine particles, polymer fine particles, pigments, defoamers, viscosity modifiers, leveling agents, flame retardants, and storage stabilizers. You may.
本発明の不飽和基含有アルカリ現像性樹脂は、高い現像性を有し、硬化物における耐熱性と誘電特性とに優れることから、ソルダーレジスト用途に好適に用いることができる。 The unsaturated group-containing alkaline developable resin of the present invention has high developability and is excellent in heat resistance and dielectric properties in a cured product, and thus can be suitably used for solder resist applications.
本発明のソルダーレジスト用樹脂材料は、例えば、前記不飽和基含有アルカリ現像性樹脂、光重合開始剤及び各種の添加剤に加え、硬化剤、硬化促進剤、有機溶媒等の各成分を含んでなる。 The resin material for solder resist of the present invention contains, for example, each component such as a curing agent, a curing accelerator, and an organic solvent in addition to the unsaturated group-containing alkaline developable resin, a photopolymerization initiator and various additives. Become.
前記硬化剤は、前記不飽和基含有アルカリ現像性樹脂中のカルボキシ基と反応し得る官能基を有するものであれば特に制限されず、例えば、エポキシ樹脂が挙げられる。ここで用いるエポキシ樹脂は、例えば、ビスフェノール型エポキシ樹脂、フェニレンエーテル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。これらのエポキシ樹脂の中でも、硬化物における耐熱性に優れることから、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂が好ましく、軟化点が５０〜１２０℃の範囲であるものが特に好ましい。 The curing agent is not particularly limited as long as it has a functional group capable of reacting with a carboxy group in the unsaturated group-containing alkaline developable resin, and examples thereof include an epoxy resin. The epoxy resin used here is, for example, a bisphenol type epoxy resin, a phenylene ether type epoxy resin, a naphthylene ether type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin. , Bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol Additive reaction type epoxy resin and the like can be mentioned. Each of these may be used alone, or two or more types may be used in combination. Among these epoxy resins, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, because they are excellent in heat resistance in cured products. , Naftor-cresol co-shrinked novolak type epoxy resin and other novolak type epoxy resins are preferable, and those having a softening point in the range of 50 to 120 ° C. are particularly preferable.
前記硬化促進剤は、前記硬化剤の硬化反応を促進するものであり、前記硬化剤としてエポキシ樹脂を用いる場合には、リン系化合物、第３級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。硬化促進剤の添加量は、例えば、前記硬化剤１００質量部に対し１〜１０質量部の範囲で用いる。 The curing accelerator accelerates the curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, a phosphorus compound, a tertiary amine, an imidazole, an organic acid metal salt, a Lewis acid, etc. Amine complex salt and the like can be mentioned. Each of these may be used alone, or two or more types may be used in combination. The amount of the curing accelerator added is, for example, in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent.
前記有機溶媒は、前記不飽和基含有アルカリ現像性樹脂や硬化剤等の各種成分を溶解し得るものであれば特に限定されず、例えば、メチルエチルケトン、アセトン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、シクロヘキサノン、メチルセロソルブ、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。
The organic solvent is not particularly limited as long as it can dissolve various components such as the unsaturated group-containing alkaline developable resin and a curing agent, and for example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, and the like. Cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and the like can be mentioned.
本発明のソルダーレジスト用樹脂材料を用いてレジスト部材を得る方法は、例えば、前記ソルダーレジスト用樹脂材料を基材上に塗布し、６０〜１００℃程度の温度範囲で有機溶剤を揮発乾燥させた後、所望のパターンが形成されたフォトマスクを通して紫外線や電子線等にて露光させ、アルカリ水溶液にて未露光部を現像し、更に１４０〜１８０℃程度の温度範囲で加熱硬化させる方法が挙げられる。 In the method of obtaining a resist member using the solder resist resin material of the present invention, for example, the solder resist resin material is applied onto a substrate, and an organic solvent is volatilized and dried in a temperature range of about 60 to 100 ° C. After that, a method of exposing with ultraviolet rays, electron beams, etc. through a photomask in which a desired pattern is formed, developing an unexposed portion with an alkaline aqueous solution, and further heating and curing in a temperature range of about 140 to 180 ° C. can be mentioned. ..
以下に、実施例および比較例をもって本発明をより詳しく説明する。
なお、実施例で得た不飽和基含有アルカリ現像性樹脂のＧＰＣチャートは、下記条件のゲルパーミエーションクロマトグラフ（ＧＰＣ）にて測定した。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The GPC chart of the unsaturated group-containing alkaline developable resin obtained in Examples was measured by a gel permeation chromatograph (GPC) under the following conditions.
測定装置 ：東ソー株式会社製「ＨＬＣ−８２２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ５０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
検出器： ＲＩ（示差屈折径）
データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルIIバージョン４．１０」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８０２０モデルIIバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G5000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Corporation
Measurement conditions:
Developing solvent tetrahydrofuran
Flow velocity 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Version 4.10".
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A solution of 1.0% by mass in terms of resin solid content in tetrahydrofuran filtered with a microfilter (50 μl).
本願実施例において不飽和基含有アルカリ現像性樹脂の酸価はＪＩＳ Ｋ ００７０（１９９２）の中和滴定法にて測定した。 In the examples of the present application, the acid value of the unsaturated group-containing alkaline developable resin was measured by the neutralization titration method of JIS K 0070 (1992).
製造例１ エポキシ樹脂（ａ１）の製造
温度計、滴下ロート、冷却管、分留管、撹拌器を取り付けたフラスコに、２，７−ジヒドロキシナフタレンを２４０質量部（１．５０モル）、３７質量％ホルムアルデヒド水溶液８５質量部（１．０５モル）、イソプロピルアルコール３７６質量部、４８％水酸化カリウム水溶液８８質量部（０．７５モル）を仕込み、室温下、窒素を吹き込みながら撹拌した。その後、７５℃に昇温し２時間攪拌した。反応終了後、第１リン酸ソーダ１０８質量部を添加して中和した後、イソプロピルアルコールを減圧下除去し、メチルイソブチルケトン４８０質量部を加えた。得られた有機層を水２００質量部で３回水洗を繰り返した後に、メチルイソブチルケトンを加熱減圧下に除去して水酸基当量は８４ｇ/当量のフェノール樹脂中間体２４５質量部を得た。次いで、温度計、冷却管、撹拌器を取り付けたフラスコに窒素ガスパージを施しながら上記反応で得られたフェノール樹脂中間体８４質量部（水酸基１．０当量）、エピクロルヒドリン４６３質量部（５．０モル）、ｎ−ブタノール５３質量部を仕込み溶解させた。５０℃に昇温した後に、２０％水酸化ナトリウム水溶液２２０質量部（１．１０モル）を３時間要して添加し、その後更に５０℃で１時間反応させた。反応終了後、１５０℃減圧下で未反応エピクロルヒドリンを留去した。得られた粗生成物にメチルイソブチルケトン３００質量部とｎ−ブタノール５０質量部とを加え溶解させた。更にこの溶液に１０質量％水酸化ナトリウム水溶液１５質量部を添加して８０℃で２時間反応させた後に洗浄液のｐＨが中性となるまで水１００質量部で水洗を３回繰り返した。次いで共沸によって系内を脱水し、精密濾過を経た後に、溶媒を減圧下で留去して目的のエポキシ樹脂（ａ１）１２６質量部を得た。エポキシ樹脂（ａ１）の軟化点は９５℃（Ｂ＆Ｒ法）、溶融粘度（測定法：ＩＣＩ粘度計法、測定温度：１５０℃）は９．０ｄＰａ・ｓ、エポキシ当量は１７２ｇ/当量であった。Ｃ１３ＮＭＲチャートにて２０３ｐｐｍ付近にカルボニル基の存在を示すピークを確認した。また、ＭＳスペクトルにて下記構造式で表される化合物の存在を示す５１２のピークを確認した。
Production Example 1 Production of epoxy resin (a1) 240 parts by mass (1.50 mol) of 2,7-dihydroxynaphthalene in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer, 37 mass 85 parts by mass (1.05 mol) of the% formaldehyde aqueous solution, 376 parts by mass of isopropyl alcohol, and 88 parts by mass (0.75 mol) of the 48% potassium hydroxide aqueous solution were charged, and the mixture was stirred at room temperature while blowing nitrogen. Then, the temperature was raised to 75 ° C. and the mixture was stirred for 2 hours. After completion of the reaction, 108 parts by mass of sodium primary phosphate was added for neutralization, isopropyl alcohol was removed under reduced pressure, and 480 parts by mass of methyl isobutyl ketone was added. The obtained organic layer was washed with 200 parts by mass of water three times, and then methyl isobutyl ketone was removed under heating and reduced pressure to obtain 245 parts by mass of a phenol resin intermediate having a hydroxyl group equivalent of 84 g / equivalent. Next, 84 parts by mass (1.0 equivalent of hydroxyl group) of the phenol resin intermediate obtained by the above reaction and 463 parts by mass (5.0 mol) of epichlorohydrin obtained by the above reaction while performing nitrogen gas purging on a flask equipped with a thermometer, a cooling tube and a stirrer. ), 53 parts by mass of n-butanol was charged and dissolved. After the temperature was raised to 50 ° C., 220 parts by mass (1.10 mol) of a 20% aqueous sodium hydroxide solution was added over 3 hours, and then the reaction was further carried out at 50 ° C. for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. To the obtained crude product, 300 parts by mass of methyl isobutyl ketone and 50 parts by mass of n-butanol were added and dissolved. Further, 15 parts by mass of a 10 mass% sodium hydroxide aqueous solution was added to this solution and reacted at 80 ° C. for 2 hours, and then washing with 100 parts by mass of water was repeated 3 times until the pH of the washing solution became neutral. Next, the inside of the system was dehydrated by azeotrope, and after undergoing microfiltration, the solvent was distilled off under reduced pressure to obtain 126 parts by mass of the target epoxy resin (a1). The softening point of the epoxy resin (a1) was 95 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) was 9.0 dPa · s, and the epoxy equivalent was 172 g / equivalent. On the C13 NMR chart, a peak indicating the presence of a carbonyl group was confirmed around 203 ppm. In addition, 512 peaks indicating the presence of the compound represented by the following structural formula were confirmed in the MS spectrum.
実施例１ 不飽和基含有アルカリ現像性樹脂（１）の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、ジエチレングリコールモノエチルエーテルアセテート１４４質量部を入れ、先で得たエポキシ樹脂（ａ１）３４４質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．４質量部、熱重合禁止剤としてメトキノン０．３質量部加えた後、アクリル酸７５質量部、無水メタクリル酸（純度９４質量％）１５７質量部、トリフェニルフォスフィン２．９質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行なった。その後、ジエチレングリコールモノエチルエーテルアセテート１７１質量部、テトラヒドロ無水フタル酸１５８質量部を加え１１０℃で５時間反応し、不飽和基含有アルカリ現像性樹脂（１）溶液（固形分７０質量％）を得た。不飽和基含有アルカリ現像性樹脂（１）の固形分酸価は８０ｍｇＫＯＨ/ｇであった。不飽和基含有アルカリ現像性樹脂（１）のＧＰＣチャート図を図１に示す。
Example 1 Production of unsaturated group-containing alkaline developable resin (1) 144 parts by mass of diethylene glycol monoethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and the epoxy resin obtained above (1). a1) After dissolving 344 parts by mass and adding 1.4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of methquinone as a thermal polymerization inhibitor, 75 parts by mass of acrylic acid and 94 parts by mass of methacrylic anhydride (purity 94 parts by mass). %) 157 parts by mass and 2.9 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Then, 171 parts by mass of diethylene glycol monoethyl ether acetate and 158 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an unsaturated group-containing alkaline developable resin (1) solution (solid content 70% by mass). .. The solid acid value of the unsaturated group-containing alkaline developable resin (1) was 80 mgKOH / g. A GPC chart of the unsaturated group-containing alkaline developable resin (1) is shown in FIG.
実施例２ 不飽和基含有アルカリ現像性樹脂（２）の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、ジエチレングリコールモノエチルエーテルアセテート１４９質量部を入れ、先で得たエポキシ樹脂（ａ１）３４４質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．５質量部、熱重合禁止剤としてメトキノン０．３質量部加えた後、アクリル酸５９質量部、無水メタクリル酸（純度９４質量％）１９３質量部、トリフェニルフォスフィン３．０質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行なった。その後、ジエチレングリコールモノエチルエーテルアセテート１６０質量部、テトラヒドロ無水フタル酸１２５質量部を加え１１０℃で５時間反応し、不飽和基含有アルカリ現像性樹脂（２）溶液（固形分７０質量％）を得た。不飽和基含有アルカリ現像性樹脂（２）の固形分酸価は６５ｍｇＫＯＨ/ｇであった。不飽和基含有アルカリ現像性樹脂（２）のＧＰＣチャート図を図２に示す。
Example 2 Production of unsaturated group-containing alkaline developable resin (2) 149 parts by mass of diethylene glycol monoethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler to obtain the epoxy resin (2) obtained above. a1) After dissolving 344 parts by mass and adding 1.5 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of methquinone as a thermal polymerization inhibitor, 59 parts by mass of acrylic acid and 94 parts by mass of methacrylic anhydride (purity 94 parts by mass). %) 193 parts by mass and 3.0 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Then, 160 parts by mass of diethylene glycol monoethyl ether acetate and 125 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an unsaturated group-containing alkaline developable resin (2) solution (solid content 70% by mass). .. The solid acid value of the unsaturated group-containing alkaline developable resin (2) was 65 mgKOH / g. A GPC chart of the unsaturated group-containing alkaline developable resin (2) is shown in FIG.
実施例３ 不飽和基含有アルカリ現像性樹脂（３）の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、ジエチレングリコールモノエチルエーテルアセテート１５４質量部を入れ、先で得たエポキシ樹脂（ａ１）３４４質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．５質量部、熱重合禁止剤としてメトキノン０．３質量部加えた後、アクリル酸４５質量部、無水メタクリル酸（純度９４質量％）２２６質量部、トリフェニルフォスフィン３．１質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行なった。その後、ジエチレングリコールモノエチルエーテルアセテート１５０質量部、テトラヒドロ無水フタル酸９４質量部を加え１１０℃で５時間反応し、不飽和基含有アルカリ現像性樹脂（３）溶液（固形分７０質量％）を得た。不飽和基含有アルカリ現像性樹脂（３）の固形分酸価は５０ｍｇＫＯＨ/ｇであった。
Example 3 Production of unsaturated group-containing alkaline developable resin (3) 154 parts by mass of diethylene glycol monoethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler to obtain the epoxy resin (3) obtained above. a1) Dissolve 344 parts by mass, add 1.5 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of methquinone as a thermal polymerization inhibitor, and then add 45 parts by mass of acrylic acid and methacrylic anhydride (purity 94 parts by mass). %) 226 parts by mass and 3.1 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Then, 150 parts by mass of diethylene glycol monoethyl ether acetate and 94 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an unsaturated group-containing alkaline developable resin (3) solution (solid content 70% by mass). .. The solid acid value of the unsaturated group-containing alkaline developable resin (3) was 50 mgKOH / g.
実施例４ 不飽和基含有アルカリ現像性樹脂（４）の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、ジエチレングリコールモノエチルエーテルアセテート１４６質量部を入れ、先で得たエポキシ樹脂（ａ１）３４４質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．５質量部、熱重合禁止剤としてメトキノン０．３質量部加えた後、アクリル酸６９質量部、無水メタクリル酸（純度９４質量％）１７０質量部、トリフェニルフォスフィン２．９質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行なった。その後、ジエチレングリコールモノエチルエーテルアセテート１４５質量部、無水コハク酸９６質量部を加え１１０℃で５時間反応し、不飽和基含有アルカリ現像性樹脂（４）溶液（固形分７０質量％）を得た。不飽和基含有アルカリ現像性樹脂（４）の固形分酸価は８０ｍｇＫＯＨ/ｇであった。
Example 4 Production of Unsaturated Group-Containing Alkaline Developable Resin (4) 146 parts by mass of diethylene glycol monoethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler to obtain the epoxy resin (4). a1) After dissolving 344 parts by mass and adding 1.5 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of methquinone as a thermal polymerization inhibitor, 69 parts by mass of acrylic acid and 94 parts by mass of methacrylic anhydride (purity 94 parts by mass). %) 170 parts by mass and 2.9 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Then, 145 parts by mass of diethylene glycol monoethyl ether acetate and 96 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an unsaturated group-containing alkaline developable resin (4) solution (solid content 70% by mass). The solid acid value of the unsaturated group-containing alkaline developable resin (4) was 80 mgKOH / g.
実施例５ 不飽和基含有アルカリ現像性樹脂（５）の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、ジエチレングリコールモノエチルエーテルアセテート１５０質量部を入れ、先で得たエポキシ樹脂（ａ１）３４４質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．５質量部、熱重合禁止剤としてメトキノン０．３質量部加えた後、アクリル酸５６質量部、無水メタクリル酸（純度９４質量％）２００質量部、トリフェニルフォスフィン３．０質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行なった。その後、ジエチレングリコールモノエチルエーテルアセテート１４１質量部、無水コハク酸７８質量部を加え１１０℃で５時間反応し、不飽和基含有アルカリ現像性樹脂（５）溶液（固形分７０質量％）を得た。不飽和基含有アルカリ現像性樹脂（５）の固形分酸価は６５ｍｇＫＯＨ/ｇであった。不飽和基含有アルカリ現像性樹脂（５）のＧＰＣチャート図を図３に示す。
Example 5 Production of unsaturated group-containing alkaline developable resin (5) 150 parts by mass of diethylene glycol monoethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler to obtain the epoxy resin (5). a1) After dissolving 344 parts by mass and adding 1.5 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of methquinone as a thermal polymerization inhibitor, 56 parts by mass of acrylic acid and 94 parts by mass of methacrylic anhydride (purity 94 parts by mass). %) 200 parts by mass and 3.0 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Then, 141 parts by mass of diethylene glycol monoethyl ether acetate and 78 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an unsaturated group-containing alkaline developable resin (5) solution (solid content 70% by mass). The solid acid value of the unsaturated group-containing alkaline developable resin (5) was 65 mgKOH / g. A GPC chart of the unsaturated group-containing alkaline developable resin (5) is shown in FIG.
実施例６ 不飽和基含有アルカリ現像性樹脂（６）の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、ジエチレングリコールモノエチルエーテルアセテート１５４質量部を入れ、先で得たエポキシ樹脂（ａ１）３４４質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．５質量部、熱重合禁止剤としてメトキノン０．３質量部加えた後、アクリル酸４３質量部、無水メタクリル酸（純度９４質量％）２２９質量部、トリフェニルフォスフィン３．０質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行なった。その後、ジエチレングリコールモノエチルエーテルアセテート１３６質量部、無水コハク酸６０質量部を加え１１０℃で５時間反応し、不飽和基含有アルカリ現像性樹脂（５）溶液（固形分７０質量％）を得た。不飽和基含有アルカリ現像性樹脂（５）の固形分酸価は５０ｍｇＫＯＨ/ｇであった。
Example 6 Production of Unsaturated Group-Containing Alkaline Developable Resin (6) 154 parts by mass of diethylene glycol monoethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler to obtain the epoxy resin (6). a1) After dissolving 344 parts by mass and adding 1.5 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of methquinone as a thermal polymerization inhibitor, 43 parts by mass of acrylic acid and 94 parts by mass of methacrylic anhydride (purity 94 parts by mass). %) 229 parts by mass and 3.0 parts by mass of triphenylphosphine were added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Then, 136 parts by mass of diethylene glycol monoethyl ether acetate and 60 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 5 hours to obtain an unsaturated group-containing alkaline developable resin (5) solution (solid content 70% by mass). The solid acid value of the unsaturated group-containing alkaline developable resin (5) was 50 mgKOH / g.
比較製造例１ 不飽和基含有アルカリ現像性樹脂（１’）の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、ジエチレングリコールモノエチルエーテルアセテート１５７質量部を入れ、オルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製『ＥＰＩＣＬＯＮ Ｎ−６９５』エポキシ当量２１５ｇ/当量）４３０質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．６質量部、熱重合禁止剤としてハイドロキノン０．３質量部を加えた後、アクリル酸１０１質量部、無水メタクリル酸（純度９４質量％）９８質量部、トリフェニルフォスフィン３．１質量部を添加し、空気を吹き込みながら１２０℃で８時間反応させた。次いで、ジエチレングリコールモノエチルエーテルアセテート２８０質量部、テトラヒドロ無水フタル酸１８２質量部を加え１１０℃で２．５時間反応させ、不飽和基含有アルカリ現像性樹脂（１’）溶液（固形分６５質量％）を得た。不飽和基含有アルカリ現像性樹脂（１’）の固形分酸価は８５ｍｇＫＯＨ/ｇであった。
Comparative Production Example 1 Production of Unsaturated Group-Containing Alkaline Developable Resin (1') 157 parts by mass of diethylene glycol monoethyl ether acetate was placed in a flask equipped with a thermometer, a stirrer, and a reflux cooler, and an orthocresol novolac type epoxy was placed. Dissolve 430 parts by mass of resin ("EPICLON N-695" manufactured by DIC Co., Ltd., epoxy equivalent 215 g / equivalent), and add 1.6 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.3 parts by mass of hydroquinone as a thermal polymerization inhibitor. After the addition, 101 parts by mass of acrylic acid, 98 parts by mass of anhydrous methacrylic acid (purity 94% by mass), and 3.1 parts by mass of triphenylphosphine were added, and the mixture was reacted at 120 ° C. for 8 hours while blowing air. Next, 280 parts by mass of diethylene glycol monoethyl ether acetate and 182 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain an unsaturated group-containing alkaline developable resin (1') solution (solid content 65% by mass). Got The solid acid value of the unsaturated group-containing alkaline developable resin (1') was 85 mgKOH / g.
実施例７〜１２及び比較例１
下記要領で光硬化型アルカリ現像性樹脂組成物を調整し、硬化物の耐熱性と、光感度、乾燥管理幅を評価した。結果を表１に示す。
Examples 7 to 12 and Comparative Example 1
The photocurable alkaline developable resin composition was prepared in the following manner, and the heat resistance, light sensitivity, and drying control range of the cured product were evaluated. The results are shown in Table 1.
◆耐熱性の評価
・光硬化型アルカリ現像性樹脂組成物の調整
先で得た不飽和基含有アルカリ現像性樹脂溶液１００質量部、硬化剤としてオルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製『ＥＰＩＣＬＯＮ Ｎ−６８０』）２４質量部、光重合開始剤として２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン（ＢＡＳＦ社製『イルガキュア９０７』）５．０質量部、硬化促進剤として２−エチル−４−メチルイミダゾール０．５質量部、有機溶剤としてジエチレングリコールモノエチルエーテルアセテート１３質量部を配合し光硬化型アルカリ現像性樹脂組成物を得た。
◆ Evaluation of heat resistance ・ Adjustment of photocurable alkaline
・硬化物の作成
ガラス基材上に先で得た光硬化型アルカリ現像性樹脂組成物を１５２μｍのアプリケーターで塗布し、８０℃で３０分間乾燥させた。次いで、メタルハライドランプを用いて１０００ｍＪ/ｃｍ２の紫外線を照射した後、２００℃で１時間加熱して、硬化物をガラス基材から剥離し、硬化物を得た。
-Preparation of cured product The photocurable alkaline developable resin composition obtained above was applied on a glass substrate with a 152 μm applicator and dried at 80 ° C. for 30 minutes. Then, after irradiating with an ultraviolet ray of 1000 mJ / cm 2 using a metal halide lamp, the cured product was heated at 200 ° C. for 1 hour to peel off the cured product from the glass substrate to obtain a cured product.
・ガラス転移温度（Ｔｇ）の測定
硬化物から６ｍｍ×３５ｍｍの試験片を切り出し、粘弾性測定装置（ＤＭＡ：レオメトリック社製固体粘弾性測定装置「ＲＳＡＩＩ」、引張り法：周波数１Ｈｚ、昇温速度３℃／分）を用いて、弾性率変化が最大となる（ｔａｎδ変化率が最も大きい）温度をガラス転移温度として評価した。
-Measurement of glass transition temperature (Tg) A 6 mm x 35 mm test piece is cut out from the cured product, and a viscoelasticity measuring device (DMA: Leometric solid viscoelasticity measuring device "RSAII", tensile method: frequency 1 Hz, heating rate) Using 3 ° C./min), the temperature at which the change in viscoelasticity was maximum (the rate of change in tan δ was the largest) was evaluated as the glass transition temperature.
◆光感度、乾燥管理幅の評価
・光硬化型アルカリ現像性樹脂組成物の調整
先で得た不飽和基含有アルカリ現像性樹脂溶液、硬化剤としてオルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製『ＥＰＩＣＬＯＮ Ｎ−６８０』）２４質量部、光重合開始剤として２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン（ＢＡＳＦ社製『イルガキュア９０７』）５．０質量部、硬化促進剤として２−エチル−４−メチルイミダゾール０．５質量部、有機溶剤としてジエチレングリコールモノエチルエーテルアセテート１３質量部、顔料としてフタロシアニングリーン０．６５質量部を配合し、ロールミルにより混錬して光硬化型アルカリ現像性樹脂組成物を得た。
◆ Evaluation of photosensitivity and drying control range ・ Adjustment of photocurable alkaline developable resin composition The unsaturated group-containing alkaline developable resin solution obtained above, orthocresol novolac type epoxy resin as a curing agent (manufactured by DIC Co., Ltd. EPICLON N-680 ”) 24 parts by mass, 5.0 mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (BASF's“ Irgacure 907 ”) as a photopolymerization initiator , 0.5 parts by mass of 2-ethyl-4-methylimidazole as a curing accelerator, 13 parts by mass of diethylene glycol monoethyl ether acetate as an organic solvent, and 0.65 parts by mass of phthalocyanine green as a pigment, and kneaded with a roll mill. A photocurable alkali-developable resin composition was obtained.
・光感度の測定
ガラス基材の上に先で得た光硬化型アルカリ現像性樹脂組成物を５０μｍのアプリケーターで塗布し、８０℃で３０分乾燥させた。次いで、コダック社製のステップタブレットＮｏ．２を介し、メタルハライドランプを用いて１０００ｍＪ/ｃｍ２の紫外線を照射した。これを１質量％の炭酸ナトリウム水溶液で１８０秒現像し、残存した段数で評価した。残存段数が多いほど光感度が高い。
-Measurement of photosensitivity The photocurable alkali-developable resin composition obtained above was applied onto a glass substrate with a 50 μm applicator and dried at 80 ° C. for 30 minutes. Next, Kodak's step tablet No. Ultraviolet rays of 1000 mJ / cm 2 were irradiated through 2 using a metal halide lamp. This was developed with a 1% by mass aqueous sodium carbonate solution for 180 seconds and evaluated by the number of remaining stages. The larger the number of remaining stages, the higher the light sensitivity.
・乾燥管理幅の測定
ガラス基材の上に先で得た光硬化型アルカリ現像性樹脂組成物を５０μｍのアプリケーターで塗布し、８０℃での乾燥時間がそれぞれ３０分、４０分、５０分、６０分であるサンプルを作成した。これらを１質量％の炭酸ナトリウム水溶液で１８０秒現像し、残渣が残らなかったサンプルの８０℃乾燥時間を乾燥管理幅として評価した。乾燥管理幅が長いほどアルカリ現像性に優れる。
-Measurement of drying control width The photocurable alkaline developable resin composition obtained above was applied on a glass substrate with a 50 μm applicator, and the drying time at 80 ° C. was 30 minutes, 40 minutes, and 50 minutes, respectively. A sample of 60 minutes was prepared. These were developed with a 1% by mass aqueous sodium carbonate solution for 180 seconds, and the drying time at 80 ° C. of the sample in which no residue remained was evaluated as the drying control range. The longer the drying control range, the better the alkali developability.
Claims (6)
（メタ）アクリル酸（ａ２）と、
（メタ）アクリル酸無水物（ａ３）と、
ジカルボン酸無水物（ａ４）とを必須の反応原料とする不飽和基含有アルカリ現像性樹脂であって、
前記エポキシ樹脂（ａ１）中のエポキシ基１モルに対する前記（メタ）アクリル酸（ａ２）及び前記（メタ）アクリル酸無水物（ａ３）の合計モル数が、０．９〜１．１モルの範囲であり、
前記（メタ）アクリル酸（ａ２）と前記（メタ）アクリル酸無水物（ａ３）とのモル比［（ａ２）／（ａ３）］が、０．３〜２．０の範囲であり、
前記（メタ）アクリル酸（ａ２）１モルに対する前記ジカルボン酸無水物（ａ４）のモル数が、０．９〜１．１モルの範囲であり、
前記不飽和基含有アルカリ現像性樹脂が、下記構造式（１）
の何れかで表される構造部位である。式中Ｒ１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子の何れかであり、ｎは１〜４の整数、ｍは１〜５の整数である。］
で表される分子構造を有する化合物（α）を含有し、樹脂中に存在するＸのうち少なくとも一つが前記構造式（２−１）で表される構造部位であり、少なくとも一つが前記構造式（２−２）で表される構造部位であることを特徴とする不飽和基含有アルカリ現像性樹脂。 Epoxy resin (a1) and
(Meta) acrylic acid (a2) and
(Meta) acrylic anhydride (a3) and
An unsaturated group-containing alkaline developable resin containing a dicarboxylic acid anhydride (a4) as an essential reaction raw material.
The total number of moles of the (meth) acrylic acid (a2) and the (meth) acrylic anhydride (a3) with respect to 1 mol of the epoxy group in the epoxy resin (a1) is in the range of 0.9 to 1.1 mol. And
The molar ratio [(a2) / (a3)] of the (meth) acrylic acid (a2) to the (meth) acrylic anhydride (a3) is in the range of 0.3 to 2.0.
The number of moles of the dicarboxylic acid anhydride (a4) with respect to 1 mol of the (meth) acrylic acid (a2) is in the range of 0.9 to 1.1 mol.
The unsaturated group-containing alkaline developable resin has the following structural formula (1).
It is a structural part represented by any of. In the formula, R 1 is independently any of a hydrogen atom, an alkyl group, an alkoxy group, and a halogen atom, n is an integer of 1 to 4, and m is an integer of 1 to 5. ]
It contains a compound (α) having a molecular structure represented by, and at least one of X present in the resin is a structural site represented by the structural formula (2-1), and at least one is the structural formula. An unsaturated group-containing alkaline developable resin characterized by having a structural portion represented by (2-2).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015209816 | 2015-10-26 | ||
| JP2015209816 | 2015-10-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017082193A JP2017082193A (en) | 2017-05-18 |
| JP6819104B2 true JP6819104B2 (en) | 2021-01-27 |
Family
ID=58711735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016135056A Active JP6819104B2 (en) | 2015-10-26 | 2016-07-07 | Unsaturated group-containing alkaline developable resin and resin material for solder resist |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6819104B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6541016B2 (en) * | 2017-04-06 | 2019-07-10 | Dic株式会社 | Acid group-containing (meth) acrylate resin and resin material for solder resist |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3543409B2 (en) * | 1995-03-24 | 2004-07-14 | 大日本インキ化学工業株式会社 | Active energy ray-curable epoxy acrylate resin composition |
| JPH0987346A (en) * | 1995-09-19 | 1997-03-31 | Dainippon Ink & Chem Inc | Energy ray curing epoxyacrylate resin composition |
| WO2010047169A1 (en) * | 2008-10-22 | 2010-04-29 | Dic株式会社 | Curable resin composition and cured product thereof, printed circuit board, and epoxy resin and method for producing same |
| JP2011144230A (en) * | 2010-01-13 | 2011-07-28 | Japan U-Pica Co Ltd | Polyfunctional epoxy (meth)acrylate compound and photosensitive thermosetting resin composition comprising the compound, and cured product thereof |
| KR102371057B1 (en) * | 2015-02-26 | 2022-03-07 | 디아이씨 가부시끼가이샤 | Alkali-developable resins containing unsaturated groups and resin materials for solder resists |
-
2016
- 2016-07-07 JP JP2016135056A patent/JP6819104B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017082193A (en) | 2017-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6324517B2 (en) | Unsaturated group-containing alkali developable resin and solder resist resin material | |
| JP2019151861A (en) | Curable resin and manufacturing method therefor | |
| JP6541016B2 (en) | Acid group-containing (meth) acrylate resin and resin material for solder resist | |
| JP6620923B2 (en) | (Meth) acrylate resin and resist member | |
| JP6819104B2 (en) | Unsaturated group-containing alkaline developable resin and resin material for solder resist | |
| JP7172555B2 (en) | Acid group-containing (meth)acrylate resin composition, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member | |
| JP6660575B2 (en) | Acid group-containing (meth) acrylate resin and resin material for solder resist | |
| JP6813135B1 (en) | Acid group-containing (meth) acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist and resist member | |
| JP6597164B2 (en) | Photocurable alkali-developable resin composition and cured product thereof | |
| JP7192521B2 (en) | Acid group-containing (meth)acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member | |
| JP6780809B1 (en) | Acid group-containing (meth) acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist and resist member | |
| JP7183761B2 (en) | Acid group-containing (meth)acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member | |
| JP6828410B2 (en) | Acid group-containing (meth) acrylate resin and resin material for solder resist | |
| JP6721858B2 (en) | Unsaturated group-containing alkali developable resin and resin material for solder resist | |
| JP6562249B2 (en) | (Meth) acrylate resin and resist member | |
| JP7196587B2 (en) | Acid group-containing (meth)acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member | |
| JP7264004B2 (en) | Acid group-containing (meth)acrylate resin composition, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member | |
| JP7264003B2 (en) | Epoxy (meth)acrylate resin composition, curable resin composition, cured product and article | |
| JP7215105B2 (en) | Acid group-containing (meth)acrylate resin, curable resin composition, cured product, insulating material, resin material for solder resist, and resist member | |
| JP7251449B2 (en) | Epoxy (meth)acrylate resin composition, curable resin composition, cured product and article | |
| JP2016121208A (en) | Carboxyl group-containing photosensitive compound, photosensitive resin, its cured product, resist material using them, and method for producing carboxyl group-containing photosensitive compound | |
| JP2018024848A (en) | Acid group-containing (meth) acrylate resin and resin material for solder resist |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20180220 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190606 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20190620 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200221 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200303 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20200407 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200623 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201201 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20201214 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6819104 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |