JP2013133352A - Composition for electrodeposition resin - Google Patents
Composition for electrodeposition resin Download PDFInfo
- Publication number
- JP2013133352A JP2013133352A JP2011282796A JP2011282796A JP2013133352A JP 2013133352 A JP2013133352 A JP 2013133352A JP 2011282796 A JP2011282796 A JP 2011282796A JP 2011282796 A JP2011282796 A JP 2011282796A JP 2013133352 A JP2013133352 A JP 2013133352A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- electrodeposition
- water
- pts
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 72
- 229920005989 resin Polymers 0.000 title description 34
- 239000011347 resin Substances 0.000 title description 34
- 239000000203 mixture Substances 0.000 title description 12
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 15
- 125000004103 aminoalkyl group Chemical group 0.000 claims abstract description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 9
- 239000011342 resin composition Substances 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims description 9
- 238000001035 drying Methods 0.000 abstract description 4
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 15
- 239000000758 substrate Substances 0.000 description 13
- -1 isobutanol Chemical class 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 12
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 11
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 11
- 229960002887 deanol Drugs 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000011550 stock solution Substances 0.000 description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 229920000877 Melamine resin Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004640 Melamine resin Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
- 229920003270 Cymel® Polymers 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 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
- TWYISXLZCIVDDW-UHFFFAOYSA-N 2-methyl-n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C(C)=C TWYISXLZCIVDDW-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
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- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 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
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
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- 239000011976 maleic acid Substances 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- YOZHLACIXDCHPV-UHFFFAOYSA-N n-(methoxymethyl)-2-methylprop-2-enamide Chemical compound COCNC(=O)C(C)=C YOZHLACIXDCHPV-UHFFFAOYSA-N 0.000 description 1
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
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- 239000003505 polymerization initiator Substances 0.000 description 1
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- 235000019260 propionic acid Nutrition 0.000 description 1
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- 238000012552 review Methods 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、マイクロ構造体製造に係る電着樹脂用組成物に関するものである。
マイクロ構造体とは、マイクロレンズ、LED用レンズ、太陽電池パネルの集光用マイクロレンズ、CCDやCMOSイメージセンサー用マイクロレンズ、オンチップ型マイクロレンズ、紙幣の偽造防止用マイクロレンズ、再帰反射用マイクロレンズがあり、一つの大きさは、縦、横、高さは1mm以下のものであり、これらを並べてアレイ状に使用しても構わない。
The present invention relates to an electrodeposition resin composition for manufacturing a microstructure.
Microstructures include microlenses, LED lenses, condensing microlenses for solar cell panels, microlenses for CCD and CMOS image sensors, on-chip microlenses, microlenses for preventing counterfeiting of banknotes, micros for retroreflection There is a lens, and one size is vertical, horizontal, and height is 1 mm or less. These may be arranged in an array.
ビデオカメラ、携帯電話、デジタルカメラ等に使用するCCD、CMOSイメージセンサーは、シリコンウエハ上にフォトダイオードによる受光素子を作製し、その上にカラーフィルタとマイクロレンズを貼り合わせ形成する。受光素子は、光の明暗に反応し電気信号を発生するものであるがこれだけではカラー画像にはならないためカラーフィルタが必要になる。また、受光素子に効率良く集光させるためにはマイクロレンズが必要となる。受光素子とカラーフィルタ間には、電気配線層が存在し集光効率を下げる要因の1つになっているが、この課題はマイクロレンズを着色することでカラーフィルタと一体化し、電気配線層を受光素子の反対側に形成することにより解決可能である。 In CCD and CMOS image sensors used in video cameras, mobile phones, digital cameras, etc., a light receiving element using a photodiode is formed on a silicon wafer, and a color filter and a microlens are bonded to each other. The light receiving element generates an electrical signal in response to the light and darkness of light. However, a color image is necessary because it does not form a color image by itself. In addition, a microlens is required to efficiently collect light on the light receiving element. There is an electrical wiring layer between the light receiving element and the color filter, which is one of the factors that reduce the light collection efficiency. However, this problem is integrated with the color filter by coloring the microlens. It can be solved by forming it on the opposite side of the light receiving element.
マイクロ構造体を形成する方法には、レジストに電子線を照射して直接形成する方法、インクジェットを用いる方法あるいは電着を用いる方法等がある(特許文献1)。
電着法でマイクロ構造体を形成する方法は、ITO基板、シリコンウエハ等の導電性基板上にドライフィルムレジスト、電着レジスト、液状レジスト等の感光性樹脂を塗布してフォトリソグラフィ法により所定のパターンを形成し、次いで電着樹脂を塗布することで形成される。しかし、どのような電着樹脂でも電着塗布して焼付乾燥するだけでマイクロ構造体を形成できる訳では無く、一般的な電着樹脂では半球状のマイクロレンズ形状を得るには電着・焼付乾燥後に樹脂が流動したり、レベリング不足により塗膜表面が凹凸になるなど均一な形状にできない場合が多く発生し、更に、シリコンウエハ上への電着では、シリコンウエハの表面張力により電着樹脂のハジキが発生し均一に塗布できないため、シリコンウエハ上でのマイクロ構造体作製が困難であった。
As a method for forming a microstructure, there are a method in which a resist is directly formed by irradiating an electron beam, a method using ink jet, a method using electrodeposition, and the like (Patent Document 1).
A method for forming a microstructure by an electrodeposition method is a method in which a photosensitive resin such as a dry film resist, an electrodeposition resist, or a liquid resist is applied on a conductive substrate such as an ITO substrate or a silicon wafer, and a predetermined method is applied by a photolithography method. It is formed by forming a pattern and then applying an electrodeposition resin. However, it is not possible to form a microstructure by simply electrodepositing and baking and drying with any electrodeposition resin, and with general electrodeposition resins, electrodeposition and baking are required to obtain a hemispherical microlens shape. In many cases, the resin flows after drying, or the surface of the coating film becomes uneven due to insufficient leveling and cannot be made into a uniform shape. Furthermore, in electrodeposition onto a silicon wafer, the electrodeposition resin is caused by the surface tension of the silicon wafer. Therefore, it was difficult to produce a micro structure on a silicon wafer.
本発明は、前記したような従来技術における問題点を解決し、複雑な製造工程を用いず、電着塗布後に焼付乾燥加熱するのみでマイクロ構造体の形成が可能であり、更に着色することでカラーフィルタの機能を備えたマイクロレンズ作製が可能で、かつシリコンウエハ上に良好な形状のマイクロ構造体を形成できる電着樹脂用組成物を提供することを目的とする。 The present invention solves the problems in the prior art as described above, and does not use a complicated manufacturing process, and it is possible to form a microstructure by simply baking and heating after electrodeposition coating. An object of the present invention is to provide a composition for an electrodeposition resin capable of producing a microlens having a color filter function and capable of forming a microstructure with a good shape on a silicon wafer.
上記問題点に対して鋭意研究の結果、本願発明者らは、電着用樹脂組成物における樹脂成分として、特定のガラス転位温度Tgと溶解性パラメータSP値とを有し、置換基としてカルボキシル基又は3級アミノアルキル基を有する単量体成分及び置換基として水酸基を有する単量体成分を含む共重合体(A)と硬化剤(B)とを含有する電着樹脂用組成物
を用いて電着塗装を行なうことにより、上記課題を克服できることを見出し、本願発明にいたった。
すなわち本発明は、(A)以下の(a)〜(c)成分を共重合することにより得られるカルボキシル基又は3級アミノアルキル基を有する水溶性又は水分散性ビニル系共重合体であって、そのガラス転位温度Tgが0〜20℃の範囲であり、溶解性パラメーターSP値が9.0〜9.5の範囲である共重合体 60〜95重量部、
(a)カルボキシル基又は3級アミノアルキル基を有する共重合性ビニル系単量体 2〜15重量部、
(b)水酸基を有する共重合性ビニル系単量体 2〜15重量部、
(c)(a)(b)以外の共重合性ビニル系単量体 70〜96重量部、
(B)硬化剤 5〜40重量部、
から成ることを特徴とするマイクロ構造体の製造に用いる電着用樹脂組成物である。
As a result of earnest research on the above problems, the present inventors have a specific glass transition temperature Tg and a solubility parameter SP value as a resin component in the electrodeposition resin composition, and a carboxyl group or a substituent as a substituent. Electrodeposition using a composition for an electrodeposition resin containing a monomer component having a tertiary aminoalkyl group and a copolymer (A) containing a monomer component having a hydroxyl group as a substituent and a curing agent (B). The inventors have found that the above-mentioned problems can be overcome by performing the coating and arrived at the present invention.
That is, the present invention is a water-soluble or water-dispersible vinyl copolymer having a carboxyl group or a tertiary aminoalkyl group obtained by copolymerizing the following components (a) to (c): 60 to 95 parts by weight of a copolymer having a glass transition temperature Tg in the range of 0 to 20 ° C. and a solubility parameter SP value in the range of 9.0 to 9.5,
(A) 2-15 parts by weight of a copolymerizable vinyl monomer having a carboxyl group or a tertiary aminoalkyl group,
(B) 2-15 parts by weight of a copolymerizable vinyl monomer having a hydroxyl group,
(C) 70 to 96 parts by weight of a copolymerizable vinyl monomer other than (a) and (b)
(B) 5 to 40 parts by weight of a curing agent,
It is an electrodeposition resin composition used for manufacture of the microstructure characterized by comprising.
ここで、ビニル系共重合体のガラス転位温度Tgは、使用する単量体のTg値より求めることが出来る。例えば、成書では北岡協三著、新高分子文庫7 塗料用合成樹脂入門(高分子刊行会)に記載されている値を用いて、以下の式より算出した。
ビニル系共重合体の1/Tg値=1/Tg1×Wt1+1/Tg2×Wt2+・・・+1/Tgn×Wtn
上式中のTg1、Tg2、・・・Tgnは成書に記載の各単量体のTg値、Wt1、Wt2、
・・・
Wtnは各単量体の総量に対する質量分率である。
Here, the glass transition temperature Tg of the vinyl copolymer can be determined from the Tg value of the monomer used. For example, in the book, the values described in Kyozo Kitaoka, New Polymer Bunko 7 Introduction to Synthetic Resins for Paints (Polymer Publications) were used to calculate from the following formula.
1 / Tg value of vinyl copolymer = 1 / Tg1 × Wt1 + 1 / Tg2 × Wt2 +++ 1 / Tgn × Wtn
In the above formulas, Tg1, Tg2,... Tgn are the Tg values of the monomers described in the text, Wt1, Wt2,
...
Wtn is a mass fraction with respect to the total amount of each monomer.
また、溶解性パラメーターSP値(σ)は、使用する単量体についてFedorsの溶解性パラメーター算出式(R.F.Fedors,Polym.Eng.Sci.,14[2]147(1974) 具体的数値は、材料技術研究協会編「実用版プラスチックのコーティング技術総覧」97〜138頁に記載されている。)を用いて計算した。
δ=(ΔE/V)1/2=(ΣΔe1/ΣΔv1)1/2
ΔE:凝集エネルギー
V:モル体積
Δe1:原子又は原子団の蒸発エネルギー
Δv1:原子又は原子団のモル体積
次に、次式によりビニル系共重合体のSP値を算出した。
ビニル系共重合体のSP値=δ1×Wt1+δ2×Wt2+…+δn×Wtn
上式中のδ1、δ2、…δnは算出された各単量体のδ値、Wt1、Wt2、・・・Wtnは各単量体の総量に対する質量分率である。
以上のとおり、本発明で使用する特定のガラス転位温度Tg範囲及び溶解性パラメーターSP値(σ)範囲を有する水溶性又は水分散性ビニル系共重合体は、単量体のTg及びSP値(σ)を参考に使用する単量体を適宜組合わせることにより合成することができる。
Further, the solubility parameter SP value (σ) is a specific numerical value of Fedors solubility parameter calculation formula (R. F. Fedors, Polym. Eng. Sci., 14 [2] 147 (1974) for the monomers used. Was calculated using the "Technical Review of Coating Technology for Practical Versions" pages 97 to 138, edited by Material Technology Research Association.
δ = (ΔE / V) 1/2 = (ΣΔe 1 / ΣΔv 1 ) 1/2
ΔE: Cohesive energy V: Molar volume Δe 1 : Evaporation energy of atom or atomic group Δv 1 : Molar volume of atom or atomic group Next, the SP value of the vinyl copolymer was calculated by the following formula.
SP value of vinyl copolymer = δ1 × Wt1 + δ2 × Wt2 + ... + δn × Wtn
In the above formula, δ1, δ2,... Δn are the calculated δ values of the respective monomers, and Wt1, Wt2, ... Wtn are mass fractions with respect to the total amount of the respective monomers.
As described above, the water-soluble or water-dispersible vinyl copolymer having the specific glass transition temperature Tg range and solubility parameter SP value (σ) range used in the present invention is the monomer Tg and SP value ( It can be synthesized by appropriately combining the monomers used with reference to σ).
本発明の電着樹脂用組成物は上記したような構成であり、本発明の特定のガラス転位温度Tg範囲及び溶解性パラメーターSP値(σ)範囲を有する水溶性又は水分散性ビニル系共重合体を含む電着樹脂用組成物を使用することで、再現性良くマイクロ構造体の作製ができ、シリコンウエハ上にも良好な電着塗膜を得ることができ、産業上極めて有用である。 The composition for an electrodeposition resin of the present invention is configured as described above, and is a water-soluble or water-dispersible vinyl copolymer having the specific glass transition temperature Tg range and solubility parameter SP value (σ) range of the present invention. By using a composition for electrodeposition resin containing coalescence, a microstructure can be produced with good reproducibility, and a good electrodeposition coating film can be obtained on a silicon wafer, which is extremely useful industrially.
本発明の構成と作用を説明する。本発明においては、置換基としてカルボキシル基又は3級アミノアルキル基を有する単量体成分及び置換基として水酸基を有する単量体成分を
含む水溶性又は水分散性ビニル系共重合体(A)、硬化剤(B)の各成分は、電着樹脂用組成物を得るための必須構成成分である。
(A)成分の水溶性又は水分散性のビニル系共重合体を構成する、置換基としてカルボキシル基を有する共重合性ビニル系単量体(a)としては、アクリル酸、メタクリル酸、アクリル酸ダイマー、イタコン酸、無水マレイン酸、マレイン酸、フマル酸、クロトン酸、シトラコン酸、メサコン酸等のアクリル系アニオン電着塗料に一般的に使用されるものを用いることができるがこれらに限定されない。これらの中では、アクリル酸、メタクリル酸を用いるのが望ましい。
置換基として3級アミノアルキル基を有する共重合性ビニル系単量体(a)としては、ジメチルアミノエチルアクリレート、ジメチルアミノエチルメタクリレート、ジエチルアミノエチルアクリレート、ジエチルアミノエチルメタクリレート、ジメチルアミノプロピルアクリルアミド等のアクリル系カチオン電着塗料に一般的に使用されるものを用いることができるがこれらに限定されない。
The configuration and operation of the present invention will be described. In the present invention, a water-soluble or water-dispersible vinyl copolymer (A) containing a monomer component having a carboxyl group or a tertiary aminoalkyl group as a substituent and a monomer component having a hydroxyl group as a substituent, Each component of the curing agent (B) is an essential component for obtaining a composition for an electrodeposition resin.
As the copolymerizable vinyl monomer (a) having a carboxyl group as a substituent constituting the water-soluble or water-dispersible vinyl copolymer of the component (A), acrylic acid, methacrylic acid, acrylic acid Although what is generally used for acrylic-type anion electrodeposition coating materials, such as a dimer, itaconic acid, maleic anhydride, maleic acid, fumaric acid, crotonic acid, citraconic acid, mesaconic acid, can be used, it is not limited to these. In these, it is desirable to use acrylic acid and methacrylic acid.
Examples of the copolymerizable vinyl monomer (a) having a tertiary aminoalkyl group as a substituent include acrylic resins such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and dimethylaminopropylacrylamide. Although what is generally used for a cationic electrodeposition coating material can be used, it is not limited to these.
(A)成分の水溶性又は水分散性のビニル系共重合体を構成する、置換基として水酸基を含有する単量体(b)としては、2−ヒドロキシエチルアクリレート、2−ヒドロキシエチルメタクリレート、2−ヒドロキシプロピルアクリレート、2−ヒドロキシプロピルメタクリレート、4−ヒドロキシブチルアクリレート、4−ヒドロキシブチルメタクリレート、ジエチレングリコールモノアクリレート、シクロヘキサンジメタノールモノアクリレート、シクロヘキサンジメタノールモノメタクリレート等が挙げられる。 As the monomer (b) containing a hydroxyl group as a substituent constituting the water-soluble or water-dispersible vinyl copolymer of the component (A), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2 -Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, diethylene glycol monoacrylate, cyclohexane dimethanol monoacrylate, cyclohexane dimethanol monomethacrylate and the like.
(A)成分の水溶性又は水分散性ビニル系共重合体を構成する、その他のビニル系単量体(c)としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、n−プロピルアクリレート、n−プロピルメタクリレート、イソプロピルアクリレート、イソプロピルメタクリレート、ノルマルブチルアクリレート、ノルマルブチルメタクリレート、ノルマルヘキシルアクリレート、ノルマルヘキシルメタクリレート、ノルマルヘプチルアクリレート、ノルマルヘプチルメタクリレート、2−エチルヘキシルアクリレート、2−エチルヘキシルメタクリレート、ノルマルラウリルアクリレート、ラウリルメタクリレート、ステアリルアクリレート、ステアリルメタクリレート等の炭素数約20までのアルキル基を有する同様な共重合性ビニルエステルやシクロヘキシルアクリレート、シクロヘキシルメタクリレート、イソボルニルアクリレート、イソボルニルメタクリレートなどの側鎖に脂環式炭化水素基を有する共重合性ビニルエステル系単量体、スチレン、α−メチルスチレン、α−クロロスチレン、ビニルトルエン等の芳香族基を有するビニル系単量体が使用できる。さらにアクリルアミド、N−メチロールアクリルアミド、N−メトキシメチルアクリルアミド、N−エトキシメチルアクリルアミド、N−イソブトキシメチルアクリルアミド、N−ブトキシメチルアクリルアミド、メタクリルアミド、N−メチロールメタクリルアミド、N−メトキシメチルメタクリルアミド、N−エトキシメチルメタクリルアミド、N−イソブトキシメチルメタクリルアミド、N−ブトキシメチルメタクリルアミド等の(メタ)アクリルアミド類やアクリロニトリル、酢酸ビニル等を使用することもできる。 As the other vinyl monomer (c) constituting the water-soluble or water-dispersible vinyl copolymer of the component (A), methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, normal butyl acrylate, normal butyl methacrylate, normal hexyl acrylate, normal hexyl methacrylate, normal heptyl acrylate, normal heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, normal lauryl acrylate, lauryl Alkyl having up to about 20 carbon atoms such as methacrylate, stearyl acrylate, stearyl methacrylate, etc. A copolymerizable vinyl ester monomer having an alicyclic hydrocarbon group in the side chain, such as a similar copolymerizable vinyl ester having a group, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, and isobornyl methacrylate, styrene , Vinyl monomers having an aromatic group such as α-methylstyrene, α-chlorostyrene and vinyltoluene can be used. Further, acrylamide, N-methylol acrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-isobutoxymethyl acrylamide, N-butoxymethyl acrylamide, methacrylamide, N-methylol methacrylamide, N-methoxymethyl methacrylamide, N (Meth) acrylamides such as ethoxymethyl methacrylamide, N-isobutoxymethyl methacrylamide, N-butoxymethyl methacrylamide, acrylonitrile, vinyl acetate and the like can also be used.
(A)成分の水溶性又は水分散性ビニル系共重合体は、ガラス転位温度Tgが20℃を越えると電着後の加熱乾燥時の塗膜の流動性が劣り球面状の形状は得られない。また、0℃未満であると流動性が良すぎるために平滑な塗膜となり、やはり、球面状の形状は得られない。
溶解性パラメーターSP値が9.5を越えると、シリコンウエハへ電着塗布した時に電着樹脂が基材表面ではじかれて成膜できない。一方、9.0未満であるとビニル系共重合体の水溶性又は水分散性が悪くなり、電着樹脂液の沈降分離が発生する。よって、SP値は9.0〜9.5の範囲であることが好ましく、9.3〜9.5の範囲がより好ましい。
水溶性又は水分散性ビニル系共重合体(A)成分中の、置換基としてカルボキシル基又
は3級アミノアルキル基を有する共重合性ビニル系単量体(a)の割合が2重量部未満であると液安定性が悪く、15重量部を超えると耐水性が悪くなり、塗布後水洗水で再溶解が起こり、5重量部から10重量部の範囲であることが好ましい。また、置換基として水酸基を有する共重合性ビニル系単量体(b)の割合が2重量部未満であると硬化剤(B)との架橋反応が進行し難く十分な塗膜性能が得られず、15重量部を超えると耐水性が悪くなり4重量部から12重量部の範囲であることがより好ましい。
When the glass transition temperature Tg exceeds 20 ° C, the water-soluble or water-dispersible vinyl copolymer of component (A) is inferior in the fluidity of the coating film during heat drying after electrodeposition, and a spherical shape is obtained. Absent. Moreover, since fluidity | liquidity is too good that it is less than 0 degreeC, it becomes a smooth coating film, and a spherical shape is not obtained again.
When the solubility parameter SP value exceeds 9.5, the electrodeposition resin is repelled on the surface of the base material when electrodeposition is applied to the silicon wafer, so that film formation cannot be performed. On the other hand, if it is less than 9.0, the water-soluble or water-dispersible property of the vinyl copolymer is deteriorated, and sedimentation and separation of the electrodeposition resin liquid occurs. Therefore, the SP value is preferably in the range of 9.0 to 9.5, and more preferably in the range of 9.3 to 9.5.
The proportion of the copolymerizable vinyl monomer (a) having a carboxyl group or tertiary aminoalkyl group as a substituent in the water-soluble or water-dispersible vinyl copolymer (A) component is less than 2 parts by weight. If it is, the liquid stability is poor, and if it exceeds 15 parts by weight, the water resistance is poor, and after application, re-dissolution occurs in washing water, and it is preferably in the range of 5 to 10 parts by weight. In addition, when the ratio of the copolymerizable vinyl monomer (b) having a hydroxyl group as a substituent is less than 2 parts by weight, the crosslinking reaction with the curing agent (B) is difficult to proceed and sufficient coating film performance is obtained. However, when the amount exceeds 15 parts by weight, the water resistance deteriorates, and the range of 4 to 12 parts by weight is more preferable.
(A)成分の水溶性又は水分散性ビニル系共重合体を重合する際に使用される溶剤は、一般的なものが使用できるが、水溶性又は水分散性という点からイソプロピルアルコール、ノルマルブタノール、イソブタノール等のアルコール類、エチレングリコールモノブチルエーテル、エチレングリコールモノターシャリーブチルエーテル等のセロソルブ類、プロピレングリコールモノメチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル等のプロピレングリコールエーテル類が望ましい。 なお、アセテート系溶剤は、水により加水分解を受けるため本発明で使用する溶剤には適さない。
(A)成分の水溶性又は水分散性ビニル系共重合体を重合する際に使用される重合開始剤は、アゾビスイソブチロニトリル、2,2’−アゾビス(2,4−ジメチルバレロニトリル)等のアゾ系開始剤、過酸化ベンゾイル、2,5−ジメチル−2,5−ジ(t−ブチルペルオキシ)ヘキサン等の過酸化物等が使用できる。
(A) Although the solvent used when superposing | polymerizing the water-soluble or water-dispersible vinyl copolymer of a component can use a general thing, isopropyl alcohol and normal butanol from the point of water solubility or water dispersibility. Desirable are alcohols such as isobutanol, cellosolves such as ethylene glycol monobutyl ether and ethylene glycol monotertiary butyl ether, and propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether. An acetate solvent is not suitable for the solvent used in the present invention because it is hydrolyzed by water.
The polymerization initiator used when polymerizing the water-soluble or water-dispersible vinyl copolymer of component (A) is azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile). ) -Based initiators, benzoyl peroxide, peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and the like.
(B)成分の硬化剤としては、置換基としてカルボキシル基を有するビニル系共重合性(A)の場合は、アミノ樹脂が最適であり、置換基として3級アミノアルキル基を有するビニル系共重合性(A)の場合は、ブロックイソシアネート化合物が適している。また、多官能アクリレートやエポキシド化合物、オキセタン化合物等と光重合開始剤を混合した光硬化性樹脂を使用することも可能である。
アミノ樹脂としては、メラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂等が使用できる。特にメラミン樹脂では、メチロール基の少なくとも一部を低級アルコールでアルコキシ化したアルコキシ化メラミンが好ましく、その際、低級アルコールとしては、メチルアルコール、エチルアルコール、n−プロピルアルコール、イソプロピルアルコール、n−ブチルアルコール、イソブチルアルコール等の一種または二種以上を使用できる。
As the curing agent for component (B), in the case of vinyl copolymer (A) having a carboxyl group as a substituent, an amino resin is optimal, and a vinyl copolymer having a tertiary aminoalkyl group as a substituent. In the case of the property (A), a blocked isocyanate compound is suitable. It is also possible to use a photocurable resin obtained by mixing a polyfunctional acrylate, epoxide compound, oxetane compound and the like with a photopolymerization initiator.
As the amino resin, melamine resin, benzoguanamine resin, urea resin and the like can be used. In particular, in the melamine resin, an alkoxylated melamine in which at least a part of a methylol group is alkoxylated with a lower alcohol is preferable. In this case, examples of the lower alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol. 1 type, or 2 or more types, such as isobutyl alcohol, can be used.
ブロックイソシアネート化合物としては、一般的なヘキサメチレンジイソシアネート、イソホロンジイソシアネート、これらのビウレット体、イソシアヌレート体、トリメチロールプロパンのアダクト体等をブロック化したものが使用できる。ブロック剤としては、メチルエチルケトンオキシム、ジメチルピラゾール、ε−カプロラクタム等が使用できる。
光硬化性樹脂としては、光ラジカル重合を利用するものとして多官能アクリレートにジペンタエリスリトールヘキサ及びペンタアクリレートやトリメチロールプロパントリアクリレートなどが使用でき、光重合開始剤としては2−ヒドロキシ−1−{4−[4−(2−ヒドロキシ−2−メチル−プロピオニル)−ベンジル]−フェニル}−2−メチル−プロパン−1−オンや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−オンなどが使用できる。
光カチオン重合を利用するものとしては、エポキシド化合物やオキセタン化合物が使用でき光重合開始剤としてモノスルホニウム塩等が使用できる。
水溶性又は水分散性ビニル系共重合体(A)成分は、60〜95重量部、好ましくは65〜80重量部、硬化剤(B)は、5〜40重量部、好ましくは20〜35重量部である。水溶性又は水分散性ビニル系共重合体(A)の割合が、60重量部未満では、電着樹脂液の分離沈降が発生し、95重量部を超えると十分な塗膜性能が得られない。硬化剤(B)の割合が、5重量部未満では、十分な塗膜性能が得られず、40重量部を超えると電着樹脂液の分離沈降が発生する。
As the blocked isocyanate compound, those obtained by blocking general hexamethylene diisocyanate, isophorone diisocyanate, biuret bodies, isocyanurate bodies, adduct bodies of trimethylolpropane, and the like can be used. As the blocking agent, methyl ethyl ketone oxime, dimethylpyrazole, ε-caprolactam and the like can be used.
As a photocurable resin, dipentaerythritol hexa, pentaacrylate, trimethylolpropane triacrylate, or the like can be used as a polyfunctional acrylate as one that utilizes photo radical polymerization, and 2-hydroxy-1- { 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one or 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholinopropan-1-one and the like can be used.
As those utilizing photocationic polymerization, epoxide compounds and oxetane compounds can be used, and monosulfonium salts and the like can be used as photopolymerization initiators.
The water-soluble or water-dispersible vinyl copolymer (A) component is 60 to 95 parts by weight, preferably 65 to 80 parts by weight, and the curing agent (B) is 5 to 40 parts by weight, preferably 20 to 35 parts by weight. Part. If the proportion of the water-soluble or water-dispersible vinyl copolymer (A) is less than 60 parts by weight, separation and sedimentation of the electrodeposition resin liquid occurs, and if it exceeds 95 parts by weight, sufficient coating performance cannot be obtained. . When the proportion of the curing agent (B) is less than 5 parts by weight, sufficient coating performance cannot be obtained, and when it exceeds 40 parts by weight, separation and precipitation of the electrodeposition resin liquid occurs.
本発明における水溶性又は水分散性ビニル系共重合体(A)のカルボキシル基を中和するのに用いることができる有機アミンとしては、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、トリイソプロピルアミン、モノブチルアミン、ジブチルアミン、トリブチルアミン、等のアルキルアミン類、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノ(2-ヒドロキシプロピル)アミン、ジ(2-ヒドロキシプロピル)アミン、トリ(2-ヒドロキシプロピル)アミン、ジメチルアミノエタノール、ジエチルアミノエタノール、などのアルカノールアミン類、エチレンジアミン、プロピレンジアミン、ジエチレンイミン、プロピレンイミン等のアルキレンイミン類、ピペラジン、モルホリン、ピラジン、ピリジン等が挙げられる。
中和するための有機アミンは、本発明の水溶性又は水分散性ビニル系共重合体(A)のカルボキシル基1モルに対し、有機アミンは、0.2〜0.9モル、好ましくは、0.3〜0.5モルで用いる。有機アミンが、0.2モル未満では、十分な水分散性が得られず液安定性が悪く沈降を生じやすく、0.9モル以上では、塩基性が増加するため電着時に水の電気分解によるガスが起こり塗膜中にピンホールが発生し易くなる。
Examples of the organic amine that can be used to neutralize the carboxyl group of the water-soluble or water-dispersible vinyl copolymer (A) in the present invention include monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Alkylamines such as monoisopropylamine, diisopropylamine, triisopropylamine, monobutylamine, dibutylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, mono (2-hydroxypropyl) amine, di (2-hydroxy) Propyl) amine, tri (2-hydroxypropyl) amine, dimethylaminoethanol, diethylaminoethanol, and other alkanolamines, ethylenediamine, propylenediamine, and ethylene N'imin, alkylene imine such as propylene imine, piperazine, morpholine, pyrazine, pyridine, and the like.
The organic amine for neutralization is 0.2 to 0.9 mol, preferably 1 to 1 mol of the carboxyl group of the water-soluble or water-dispersible vinyl copolymer (A) of the present invention. Used at 0.3-0.5 mol. If the organic amine is less than 0.2 mol, sufficient water dispersibility cannot be obtained and the liquid stability is poor and precipitation tends to occur. If it is 0.9 mol or more, the basicity increases, so water is electrolyzed during electrodeposition. Gas is generated and pinholes are easily generated in the coating film.
本発明における水溶性又は水分散性ビニル系共重合体(A)の3級アミノアルキル基を中和するのに用いることができる酸としては、ギ酸、酢酸、プロピオン酸、乳酸、2−エチルブタン酸、オクチル酸などの有機酸が挙げられ、3級アミノアルキル基1モルに対し、有機酸は、0.2から0.9モル、好ましくは、0.3〜0.5モルで用いる。
有機酸が、0.2モル未満では、十分な水分散性が得られず液安定性が悪く沈降を生じやすく、0.9モル以上では、酸性が増加するため電着時に水の電気分解によるガスが起こり塗膜中にピンホールが発生し易くなる。
本発明により構成される電着樹脂用組成物は基板上に電着塗装されるが、基板としてはITO膜の透明性電極、シリコンウエハなどの導電性の被膜層を有する基板や銅、アルミニウムなどの金属板が使用できる。
また、基板は、予めフォトレジストを塗布して所定のパターンを描画したフォトマスク越しに露光し更に現像して、本発明の電着樹脂を塗布する部分を限定しマイクロ構造体を形成出来るようにする。
Examples of the acid that can be used to neutralize the tertiary aminoalkyl group of the water-soluble or water-dispersible vinyl copolymer (A) in the present invention include formic acid, acetic acid, propionic acid, lactic acid, and 2-ethylbutanoic acid. Organic acids such as octylic acid and the like. The organic acid is used in an amount of 0.2 to 0.9 mol, preferably 0.3 to 0.5 mol, per 1 mol of the tertiary aminoalkyl group.
If the organic acid is less than 0.2 mol, sufficient water dispersibility cannot be obtained and the liquid stability is poor, and sedimentation tends to occur. If it is 0.9 mol or more, the acidity increases, so water is electrolyzed during electrodeposition. Gas is generated and pinholes are easily generated in the coating film.
The composition for electrodeposition resin constituted according to the present invention is electrodeposited on a substrate. As a substrate, a transparent electrode of ITO film, a substrate having a conductive coating layer such as a silicon wafer, copper, aluminum, etc. Metal plates can be used.
Further, the substrate is exposed to light through a photomask in which a predetermined pattern has been applied and a predetermined pattern is drawn, and further developed so that a portion to which the electrodeposition resin of the present invention is applied can be limited to form a microstructure. To do.
また、電着塗布条件としては、通電工程において印加される電圧は10〜200V、好ましくは20〜100Vであり、通電時間は0.1分〜10分、好ましくは0.5〜5分である。電圧が高いほど通電時間は短く、電圧が低ければ通電時間を長くする。印加電圧は通電と同時に設定電圧をかけるハードスタート、あるいは徐々に設定電圧まで電圧を上げていくソフトスタートのいずれでもかまわない。
電着塗装された被塗装物は、水洗され、次いで90℃で30分間程度加熱し、塗装膜中の水分を乾燥すると同時に電着樹脂は流動し半球状のマイクロ構造体を形成する。加熱温度は、50℃から120℃、好ましくは60℃から100℃である。50℃未満では電着樹脂の流動が起こらず、120℃以上では流動し過ぎてマイクロ構造体を形成しない。加熱時間は、20分から120分、好ましくは30分から60分である。20分未満であると水溶性又は水分散性ビニル系共重合体(A)と硬化剤(B)の反応が進行せず、120分以上ではマイクロ構造体を形成する工程時間が長くなり実用性が低下する。
また、本電着樹脂液に水性顔料を添加してマイクロ構造体を着色することも可能である。
アニオン性電着液とカチオン性電着液では、適する水性顔料がそれぞれで異なるため選定に注意が必要である。
多色化する場合は、予め基板に塗布するフォトレジストをポジ型のものを使用する。一度形成したマイクロ構造体の基板を再度所定のパターンで露光現像し異なる色に着色した電着樹脂液を塗布することを繰り返すことで可能となる。
Moreover, as electrodeposition coating conditions, the voltage applied in the energization step is 10 to 200 V, preferably 20 to 100 V, and the energization time is 0.1 to 10 minutes, preferably 0.5 to 5 minutes. . The higher the voltage, the shorter the energization time, and the lower the voltage, the longer the energization time. The applied voltage may be either a hard start in which a set voltage is applied simultaneously with energization, or a soft start in which the voltage is gradually raised to the set voltage.
The electrodeposition-coated object is washed with water and then heated at 90 ° C. for about 30 minutes to dry the water in the coating film, and at the same time, the electrodeposition resin flows to form a hemispherical microstructure. The heating temperature is 50 ° C to 120 ° C, preferably 60 ° C to 100 ° C. If it is less than 50 ° C., the electrodeposition resin does not flow, and if it is 120 ° C. or more, it flows too much to form a microstructure. The heating time is 20 minutes to 120 minutes, preferably 30 minutes to 60 minutes. If the reaction time is less than 20 minutes, the reaction between the water-soluble or water-dispersible vinyl copolymer (A) and the curing agent (B) does not proceed. If the reaction time is 120 minutes or more, the process time for forming the microstructure becomes longer. Decreases.
It is also possible to add an aqueous pigment to the electrodeposition resin liquid to color the microstructure.
The anionic electrodeposition liquid and the cationic electrodeposition liquid are different in suitable aqueous pigments, so care must be taken in selecting them.
In the case of increasing the number of colors, a positive type photoresist is applied to the substrate in advance. It becomes possible by repeating the exposure of the microstructure substrate once formed in a predetermined pattern and applying the electrodeposition resin liquid colored in a different color.
以下に本発明の実施例および比較例を挙げてさらに具体的に説明するが、これによって本発明が限定されるものではない。なお、実施例、比較例中の部は、特に断りのない限り重量部である。
製造例1
攪拌装置、還流冷却器および窒素導入管を備えた3リットルの4つ口フラスコにイソプロパノール17.25部、ブチルセロソルブ8.75部を仕込み、90℃に昇温した。別にイソプロパノール12.5部、アクリル酸5部、2−ヒドロキシエチルメタクリレート10部、スチレン10部、エチルアクリレート55部、メチルメタクリレート20部、アゾビスイソブチロニトリル1.25部の混合液を滴下ロートに仕込み、前記フラスコ内に120分かけて滴下した。滴下終了後、さらにイソプロパノール0.5部、アゾビスイソブチロニトリル0.25部を、30分毎に2回添加したのちに、さらに90℃で120分反応を続けた。得られた共重合体は、Tg19.0℃、SP値9.36であった。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited thereto. In addition, the part in an Example and a comparative example is a weight part unless there is particular notice.
Production Example 1
Into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 17.25 parts of isopropanol and 8.75 parts of butyl cellosolve were charged, and the temperature was raised to 90 ° C. Separately, 12.5 parts of isopropanol, 5 parts of acrylic acid, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of styrene, 55 parts of ethyl acrylate, 20 parts of methyl methacrylate, and 1.25 parts of azobisisobutyronitrile are added in a dropping funnel. And dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.5 part of isopropanol and 0.25 part of azobisisobutyronitrile were added twice every 30 minutes, and the reaction was further continued at 90 ° C. for 120 minutes. The obtained copolymer had a Tg of 19.0 ° C. and an SP value of 9.36.
製造例2
攪拌装置、還流冷却器および窒素導入管を備えた3リットルの4つ口フラスコにイソプロパノール17.5部、ブチルセロソルブ8.75部を仕込み、90℃に昇温した。別にイソプロパノール12.5部、アクリル酸4.5部、2−ヒドロキシエチルメタクリレート10部、スチレン10部、エチルアクリレート45部、メチルメタクリレート30.5部、アゾビスイソブチロニトリル1.25部の混合液を滴下ロートに仕込み、前記フラスコ内に120分かけて滴下した。滴下終了後、さらにイソプロパノール0.5部、アゾビスイソブチロニトリル0.25部を、30分毎に2回添加したのちに、さらに90℃で120分反応を続けた。得られた共重合体は、Tg30.8℃、SP値9.35であった。
Production Example 2
17.5 parts of isopropanol and 8.75 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, 12.5 parts of isopropanol, 4.5 parts of acrylic acid, 10 parts of 2-hydroxyethyl methacrylate, 10 parts of styrene, 45 parts of ethyl acrylate, 30.5 parts of methyl methacrylate, and 1.25 parts of azobisisobutyronitrile are mixed. The liquid was charged into a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.5 part of isopropanol and 0.25 part of azobisisobutyronitrile were added twice every 30 minutes, and the reaction was further continued at 90 ° C. for 120 minutes. The obtained copolymer had a Tg of 30.8 ° C. and an SP value of 9.35.
製造例3
攪拌装置、還流冷却器および窒素導入管を備えた3リットルの4つ口フラスコにイソプロパノール8部、ブチルセロソルブ9.6部を仕込み、90℃に昇温した。別にイソプロパノール18.4部、アクリル酸6部、2−ヒドロキシエチルアクリレート10部、2−ヒドロキシエチルメタクリレート5部、エチルアクリレート39部、メチルメタクリレート40部、アゾビスイソブチロニトリル1部の混合液を滴下ロートに仕込み、前記フラスコ内に120分かけて滴下した。滴下終了後、さらにイソプロパノール3部、アゾビスイソブチロニトリル0.25部を、30分毎に2回添加したのちに、さらに90℃で120分反応を続けた。得られた共重合体は、Tg29.1℃、SP値9.55であった。
Production Example 3
Into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, 8 parts of isopropanol and 9.6 parts of butyl cellosolve were charged, and the temperature was raised to 90 ° C. Separately, a mixed liquid of 18.4 parts of isopropanol, 6 parts of acrylic acid, 10 parts of 2-hydroxyethyl acrylate, 5 parts of 2-hydroxyethyl methacrylate, 39 parts of ethyl acrylate, 40 parts of methyl methacrylate, and 1 part of azobisisobutyronitrile. The mixture was placed in a dropping funnel and dropped into the flask over 120 minutes. After completion of the dropwise addition, 3 parts of isopropanol and 0.25 part of azobisisobutyronitrile were added twice every 30 minutes, and the reaction was further continued at 90 ° C. for 120 minutes. The obtained copolymer had a Tg of 29.1 ° C. and an SP value of 9.55.
製造例4
攪拌装置、還流冷却器および窒素導入管を備えた3リットルの4つ口フラスコにイソプロパノール10.5部、ブチルセロソルブ7部を仕込み、90℃に昇温した。別にイソプロパノール18.4部、アクリル酸6部、2−ヒドロキシエチルアクリレート15部、n−ブチルアクリレート33部、メチルメタクリレート46部、アゾビスイソブチロニトリル1部の混合液を滴下ロートに仕込み、前記フラスコ内に120分かけて滴下した。滴下終了後、さらにイソプロパノール0.3部、アゾビスイソブチロニトリル0.2部を、30分毎に3回添加したのちに、さらに90℃で120分反応を続けた。得られた共重合体は、Tg15.7℃、SP値9.55であった。
Production Example 4
10.5 parts of isopropanol and 7 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, a mixture of 18.4 parts of isopropanol, 6 parts of acrylic acid, 15 parts of 2-hydroxyethyl acrylate, 33 parts of n-butyl acrylate, 46 parts of methyl methacrylate and 1 part of azobisisobutyronitrile was charged into the dropping funnel, The solution was dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.3 part of isopropanol and 0.2 part of azobisisobutyronitrile were further added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 120 minutes. The obtained copolymer had a Tg of 15.7 ° C. and an SP value of 9.55.
製造例5
攪拌装置、還流冷却器および窒素導入管を備えた3リットルの4つ口フラスコにイソプロパノール10.5部、ブチルセロソルブ7部を仕込み、90℃に昇温した。別にイソプロパノール18.4部、アクリル酸6部、2−ヒドロキシエチルアクリレート10部、n−ブチルアクリレート50部、メチルメタクリレート34部、アゾビスイソブチロニトリ
ル1部の混合液を滴下ロートに仕込み、前記フラスコ内に120分かけて滴下した。滴下終了後、さらにイソプロパノール0.3部、アゾビスイソブチロニトリル0.2部を、30分毎に3回添加したのちに、さらに90℃で120分反応を続けた。得られた共重合体は、Tg−4.8℃、SP値9.36であった。
Production Example 5
10.5 parts of isopropanol and 7 parts of butyl cellosolve were charged into a 3 liter four-necked flask equipped with a stirrer, a reflux condenser and a nitrogen introduction tube, and the temperature was raised to 90 ° C. Separately, a mixture of 18.4 parts of isopropanol, 6 parts of acrylic acid, 10 parts of 2-hydroxyethyl acrylate, 50 parts of n-butyl acrylate, 34 parts of methyl methacrylate, and 1 part of azobisisobutyronitrile is charged into the dropping funnel, The solution was dropped into the flask over 120 minutes. After completion of the dropwise addition, 0.3 part of isopropanol and 0.2 part of azobisisobutyronitrile were further added three times every 30 minutes, and the reaction was further continued at 90 ° C. for 120 minutes. The obtained copolymer had a Tg of -4.8 ° C and an SP value of 9.36.
実施例1
製造例1で得られたビニル系共重合体141部とメラミン樹脂(日本サイテックインダストリー株式会社製 サイメル285)を42.9部、ジメチルアミノエタノール1.9部、イソプロパノール24部、ブチルセロソルブ2部を加え攪拌を続けながら脱イオン水25.3部添加して攪拌を行い電着用原液を得た。別の容器にこの電着用原液を133.3部仕込み攪拌しながら脱イオン水を866部とジメチルアミノエタノール1.7部を投入し電着樹脂液を得た。
Example 1
Add 141 parts of the vinyl copolymer obtained in Production Example 1 and 42.9 parts of melamine resin (Cymel 285, manufactured by Nippon Cytec Industry Co., Ltd.), 1.9 parts of dimethylaminoethanol, 24 parts of isopropanol, and 2 parts of butyl cellosolve. While continuing stirring, 25.3 parts of deionized water was added and stirred to obtain a stock solution for electrodeposition. In a separate container, 133.3 parts of this electrodeposition stock solution was charged, and 866 parts of deionized water and 1.7 parts of dimethylaminoethanol were added while stirring to obtain an electrodeposition resin solution.
比較例1
製造例2で得られたビニル系共重合体141.5部とメラミン樹脂(日本サイテックインダストリー株式会社製 サイメル285)を42.9部、ジメチルアミノエタノール1.7部、イソプロパノール24部、ブチルセロソルブ1.2部を加え攪拌を続けながら脱イオン水26部添加して攪拌を行い電着用原液を得た。別の容器にこの電着用原液を133.3部仕込み攪拌しながら脱イオン水を866部とジメチルアミノエタノール1.6部を投入し電着樹脂液を得た。
Comparative Example 1
142.9 parts of the vinyl copolymer obtained in Production Example 2 and 42.9 parts of melamine resin (Cymel 285 manufactured by Nippon Cytec Industry Co., Ltd.), 1.7 parts of dimethylaminoethanol, 24 parts of isopropanol, and butyl cellosolve 1. Two parts were added and 26 parts of deionized water was added while stirring, followed by stirring to obtain a stock solution for electrodeposition. In a separate container, 133.3 parts of this electrodeposition stock solution was charged, and 866 parts of deionized water and 1.6 parts of dimethylaminoethanol were added while stirring to obtain an electrodeposition resin solution.
比較例2
製造例3で得られたビニル系共重合体143.5部とメラミン樹脂(日本サイテックインダストリー株式会社製 サイメル285)を42.9部、ジメチルアミノエタノール2.2部、イソプロパノール35部、ブチルセロソルブ9部を加え攪拌を続けながら脱イオン水27部添加して攪拌を行い電着用原液を得た。別の容器にこの電着用原液を145.3部仕込み攪拌しながら脱イオン水を852.6部とジメチルアミノエタノール2.1部を投入し電着樹脂液を得た。
Comparative Example 2
142.9 parts of the vinyl copolymer obtained in Production Example 3 and 42.9 parts of melamine resin (Cymel 285 manufactured by Nippon Cytec Industry Co., Ltd.), 2.2 parts of dimethylaminoethanol, 35 parts of isopropanol, 9 parts of butyl cellosolve Then, 27 parts of deionized water was added while stirring and stirring was performed to obtain a stock solution for electrodeposition. In a separate container, 145.3 parts of this electrodeposition stock solution was charged and 852.6 parts deionized water and 2.1 parts dimethylaminoethanol were added while stirring to obtain an electrodeposition resin solution.
比較例3
製造例4で得られたビニル系共重合体138.4部とメラミン樹脂(日本サイテックインダストリー株式会社製 サイメル285)を47部、ジメチルアミノエタノール3.7部、イソプロパノール26部、ブチルセロソルブ5部を加え攪拌を続けながら脱イオン水25.4部添加して攪拌を行い電着用原液を得た。別の容器にこの電着用原液を133.6部仕込み攪拌しながら脱イオン水を865.2部とジメチルアミノエタノール1.2部を投入し電着樹脂液を得た。
Comparative Example 3
Add 138.4 parts of the vinyl copolymer obtained in Production Example 4 and 47 parts of melamine resin (Cymel 285 manufactured by Nippon Cytec Industries, Ltd.), 3.7 parts of dimethylaminoethanol, 26 parts of isopropanol, and 5 parts of butyl cellosolve. While stirring, 25.4 parts of deionized water was added and stirred to obtain a stock solution for electrodeposition. In a separate container, 133.6 parts of this stock solution for electrodeposition was charged and 865.2 parts of deionized water and 1.2 parts of dimethylaminoethanol were added while stirring to obtain an electrodeposition resin solution.
比較例4
製造例5で得られたビニル系共重合体138.4部とメラミン樹脂(日本サイテックインダストリー株式会社製 サイメル285)を47部、ジメチルアミノエタノール3.7部、イソプロパノール26部、ブチルセロソルブ5部を加え攪拌を続けながら脱イオン水25.4部添加して攪拌を行い電着用原液を得た。別の容器にこの電着用原液を133.6部仕込み攪拌しながら脱イオン水を865.2部とジメチルアミノエタノール1.2部を投入し電着樹脂液を得た。
Comparative Example 4
Add 138.4 parts of the vinyl copolymer obtained in Production Example 5 and 47 parts of melamine resin (Cymel 285 manufactured by Nippon Cytec Industries, Inc.), 3.7 parts of dimethylaminoethanol, 26 parts of isopropanol, and 5 parts of butyl cellosolve. While stirring, 25.4 parts of deionized water was added and stirred to obtain a stock solution for electrodeposition. In a separate container, 133.6 parts of this stock solution for electrodeposition was charged and 865.2 parts of deionized water and 1.2 parts of dimethylaminoethanol were added while stirring to obtain an electrodeposition resin solution.
(1)電着用基板の製造
電着用基板は、シリコンウエハ導電性基板にポジ型フォトレジストを塗布して、複数の直径100μmの円を間隔300μmで配置したパターンのフォトマスクを用い露光現像して作製した。
(2)電着樹脂用組成物の評価
実施例1、比較例1〜4で調整した電着樹脂液を使用し、常法に従って陽極に前記導電性基板を、陰極にSUS304板を用いて、10μmの塗膜厚が得られる条件で電着塗装を実施した。次いで電着塗装された基板を取り出して充分に水洗したのち、90℃の温度で30分間乾燥した。
電着塗膜が直径約100μmの半球状のマイクロレンズ形状が得られるものを○とし、半球状のマイクロレンズ形状が得られないものは×としその時の形状を評価した。
評価結果は、表1に示すとおりであった。ガラス転位温度Tgの範囲又は溶解性パラメーターSP値の範囲のいずれかが本発明の範囲を外れる電着樹脂用組成物は、実用可能なマイクロレンズ形状を得ることができなかった。
(1) Manufacture of electrodeposition substrate The electrodeposition substrate is exposed and developed using a photomask having a pattern in which a positive photoresist is applied to a silicon wafer conductive substrate and a plurality of circles having a diameter of 100 μm are arranged at intervals of 300 μm. Produced.
(2) Evaluation of composition for electrodeposition resin Using the electrodeposition resin liquid prepared in Example 1 and Comparative Examples 1 to 4, using the conductive substrate as an anode and a SUS304 plate as a cathode according to a conventional method, Electrodeposition coating was carried out under the condition that a coating thickness of 10 μm was obtained. Next, the electrodeposited substrate was taken out, washed thoroughly with water, and dried at a temperature of 90 ° C. for 30 minutes.
The case where the electrodeposition coating film obtained a semispherical microlens shape with a diameter of about 100 μm was rated as ◯, and the case where the hemispherical microlens shape could not be obtained was marked as x, and the shape at that time was evaluated.
The evaluation results are as shown in Table 1. An electrodeposition resin composition in which either the range of the glass transition temperature Tg or the range of the solubility parameter SP value is outside the range of the present invention could not obtain a practical microlens shape.
他の実施例
実施例1の電着液に水性顔料(山陽色素株式会社製、赤顔料:EMACOL SF RED GA4012、青顔料:EMACOL SF BLUE GA4011、緑顔料:EMACOL SF GREEN GA4013)を体積濃度で3%添加し3色の電着液を作製した後、緑、青、赤の順で上記方法にて電着塗布を繰り返すことにより3原色のカラーフィルターに使用可能なマイクロレンズを作製した。これらのマイクロレンズは、いずれも半球状のマイクロレンズ形状を有し、カラーフィルターとして使用可能なものであった。
Other Examples An aqueous pigment (manufactured by Sanyo Dye Co., Ltd., red pigment: EMACOL SF RED GA4012, blue pigment: EMACOL SF BLUE GA4011, green pigment: EMACOL SF GREEN GA4013) is added to the electrodeposition liquid of Example 1 at a volume concentration of 3 After adding 3% to prepare a three-color electrodeposition solution, a microlens that can be used for a three-primary-color color filter was prepared by repeating electrodeposition coating in the order of green, blue, and red. Each of these microlenses has a hemispherical microlens shape and can be used as a color filter.
本発明の電着樹脂用組成物を使用することでマイクロ構造体の作製は容易となり、顔料で着色することでカラー化も可能となり産業上極めて有用である。 By using the composition for electrodeposition resin of the present invention, it becomes easy to produce a microstructure, and coloring is possible by coloring with a pigment, which is extremely useful industrially.
Claims (2)
(a)カルボキシル基又は3級アミノアルキル基を有する共重合性ビニル系単量体 2〜15重量部、
(b)水酸基を有する共重合性ビニル系単量体 2〜15重量部、
(c)(a)(b)以外の共重合性ビニル系単量体 70〜96重量部、
(B)硬化剤 5〜40重量部、
から成ることを特徴とするマイクロ構造体の製造に用いる電着用樹脂組成物。 (A) A water-soluble or water-dispersible vinyl copolymer having a carboxyl group or a tertiary aminoalkyl group obtained by copolymerizing the following components (a) to (c), and its glass transition temperature 60-95 parts by weight of a copolymer having a Tg in the range of 0-20 ° C. and a solubility parameter SP value in the range of 9.0-9.5,
(A) 2-15 parts by weight of a copolymerizable vinyl monomer having a carboxyl group or a tertiary aminoalkyl group,
(B) 2-15 parts by weight of a copolymerizable vinyl monomer having a hydroxyl group,
(C) 70 to 96 parts by weight of a copolymerizable vinyl monomer other than (a) and (b)
(B) 5 to 40 parts by weight of a curing agent,
An electrodeposition resin composition for use in the production of a microstructure comprising:
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JP2013133389A (en) * | 2011-12-26 | 2013-07-08 | Sanyo Shikiso Kk | Pigment dispersion having specific particle charge and use of the dispersion to ionic electrodeposition liquid |
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CN111819010A (en) * | 2018-12-18 | 2020-10-23 | 日涂汽车涂料有限公司 | Cationic electrodeposition coating composition and method for forming cured electrodeposition coating film |
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