TW200914474A - Novel polymer - Google Patents
Novel polymer Download PDFInfo
- Publication number
- TW200914474A TW200914474A TW097127274A TW97127274A TW200914474A TW 200914474 A TW200914474 A TW 200914474A TW 097127274 A TW097127274 A TW 097127274A TW 97127274 A TW97127274 A TW 97127274A TW 200914474 A TW200914474 A TW 200914474A
- Authority
- TW
- Taiwan
- Prior art keywords
- polymer
- monomer
- group
- acid
- acrylate
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 56
- -1 N-substituted maleimide Chemical class 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 29
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 claims description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 26
- 239000003513 alkali Substances 0.000 abstract description 13
- 150000002170 ethers Chemical class 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 20
- 238000000576 coating method Methods 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 13
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000052 vinegar Substances 0.000 description 12
- 235000021419 vinegar Nutrition 0.000 description 12
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 9
- 238000011161 development Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000013585 weight reducing agent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 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 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- TVWXHVWKOAZBGO-UHFFFAOYSA-N CNN.C(CO)O Chemical compound CNN.C(CO)O TVWXHVWKOAZBGO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical group CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- MPTVOJQMOKMTNP-UHFFFAOYSA-N ethylbenzene;toluene Chemical group CC1=CC=CC=C1.CCC1=CC=CC=C1 MPTVOJQMOKMTNP-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Natural products CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- PUNXVEAWLAVABA-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene;1,2,5,6-tetrahydroanthracene Chemical compound C1=CC=C2C=C(CCCC3)C3=CC2=C1.C1=CCCC2=C1C=C1CCC=CC1=C2 PUNXVEAWLAVABA-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- PGRNEGLBSNLPNP-UHFFFAOYSA-N 1,6-dichloro-3-methylhex-1-ene Chemical compound ClC=CC(C)CCCCl PGRNEGLBSNLPNP-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- ZFSFKYIBIOKXKI-UHFFFAOYSA-N 1-ethyl-1-methylhydrazine Chemical compound CCN(C)N ZFSFKYIBIOKXKI-UHFFFAOYSA-N 0.000 description 1
- JQCSUVJDBHJKNG-UHFFFAOYSA-N 1-methoxy-ethyl Chemical group C[CH]OC JQCSUVJDBHJKNG-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- FZSPYHREEHYLCB-UHFFFAOYSA-N 1-tert-butyl-3,5-dimethylbenzene Chemical group CC1=CC(C)=CC(C(C)(C)C)=C1 FZSPYHREEHYLCB-UHFFFAOYSA-N 0.000 description 1
- CFGGNXFNDNQZKD-UHFFFAOYSA-N 2-(9H-fluoren-1-yl)prop-2-enoic acid Chemical compound C1C2=CC=CC=C2C2=C1C(C(=C)C(=O)O)=CC=C2 CFGGNXFNDNQZKD-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- FMWIHHOKUUJBQC-UHFFFAOYSA-N 2-hydroxyethyl 2-hydroxyprop-2-enoate Chemical compound OCCOC(=O)C(O)=C FMWIHHOKUUJBQC-UHFFFAOYSA-N 0.000 description 1
- DAWJJMYZJQJLPZ-UHFFFAOYSA-N 2-sulfanylprop-2-enoic acid Chemical compound OC(=O)C(S)=C DAWJJMYZJQJLPZ-UHFFFAOYSA-N 0.000 description 1
- WBGKAOURNYRYBT-UHFFFAOYSA-N 2-sulfopropanoic acid Chemical compound OC(=O)C(C)S(O)(=O)=O WBGKAOURNYRYBT-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- URTBROMWXOAVJQ-UHFFFAOYSA-N C(C)(=O)O.CNN.C(C(C)O)O Chemical compound C(C)(=O)O.CNN.C(C(C)O)O URTBROMWXOAVJQ-UHFFFAOYSA-N 0.000 description 1
- UOGVELIIXLCAAV-UHFFFAOYSA-N C(C)(C)(C)[C]C(C)C Chemical compound C(C)(C)(C)[C]C(C)C UOGVELIIXLCAAV-UHFFFAOYSA-N 0.000 description 1
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- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 description 1
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241001292274 Eumenes Species 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
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- 244000147568 Laurus nobilis Species 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- XQAVYBWWWZMURF-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO XQAVYBWWWZMURF-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- FSQGOCMNRFLVOO-UHFFFAOYSA-N SC(C(=O)OCC1=CC=CC=C1)=C Chemical compound SC(C(=O)OCC1=CC=CC=C1)=C FSQGOCMNRFLVOO-UHFFFAOYSA-N 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 1
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N alpha-mercaptoacetic acid Natural products OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- QNOJNOBJMMNCFZ-UHFFFAOYSA-N bromoethane;toluene Chemical compound CCBr.CC1=CC=CC=C1 QNOJNOBJMMNCFZ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- XSQNOFMFKVYSNL-UHFFFAOYSA-N ethene;toluene Chemical compound C=C.CC1=CC=CC=C1 XSQNOFMFKVYSNL-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 230000004438 eyesight Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000004519 grease Substances 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- MKIJJIMOAABWGF-UHFFFAOYSA-N methyl 2-sulfanylacetate Chemical compound COC(=O)CS MKIJJIMOAABWGF-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 229930003658 monoterpene Natural products 0.000 description 1
- 235000002577 monoterpenes Nutrition 0.000 description 1
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- PRZSXZWFJHEZBJ-UHFFFAOYSA-N thymol blue Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C PRZSXZWFJHEZBJ-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
- C08F222/402—Alkyl substituted imides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Photolithography (AREA)
Abstract
Description
200914474 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種耐熱性優異之新賴聚合物。 先前技術】 以 往，耐熱性優異之具有光聚合性之聚合物係提出例 如：將含有馬來醯亞胺之單體成分加以聚合而成之聚合物 (例如，參照曰本專利特開2003_201316號公報）、將特定 結構的化合物即2-(羥基烷基）丙烯酸酯之醚二聚物加以= 合而成之聚合物（例如，參照曰本專利特開2〇〇4·3〇〇2们 公報）等。 ^ 然而’該等聚合物在膜、薄膜之形成步驟中之加熱時 會熱分解’並產生分解氣體的情況係相當明顯。例如，使 用該等聚合物作為液晶顯示器、印刷配線基板製作用之感 光性樹脂的情況時，有於製造步驟中加熱時產生之分解物 會汙染加熱爐、或者分解物會汙毕 I亇木液晶、基板而電氣絕緣 性降低等情況。 又’有人提出馬來醯亞胺、 本乙烯、以及具有酸基之 聚合物（例如，參照曰本專利牲 特開2002-301 19號公報）等。 但是，此種聚合物有對有機、、交為丨 ra AH 有H驗之溶解速度慢的問題。 因此，係要求一種聚合物，复古 ”枚间耐熱性同時容易調製榭 脂組成物，且作為感光性 彳 尤用時可提高顯影性。 【發明内容】 5 200914474 種聚合物，其耐熱性優 對於有機溶劑、鹼之溶 因而’本發明之目的係提供一 異而可減少於加熱時產生之氣體， 解速度快，且鹼顯影性優異。 本發明人為了解決上述課題而努力探討。其結果發現 以N-取代馬來醯亞胺及/或特定結構之化合物即權基烧 基)丙烯酸酿之醚二聚物、乙烯基甲苯、以及具有酸基之單 體作為必須成分共聚合而成之高分子（p〇lymer)可一舉解決 此課題，而本發明於焉完成。 亦即本毛明之特徵在於係一種以N-取代馬來醯亞胺 及/或下述通式（1)所表示之化合物、乙烯基甲苯、以及具 有酸基之單體作為必須成分共聚合而成之高分子。200914474 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a novel lyon polymer excellent in heat resistance. In the prior art, a photopolymerizable polymer having excellent heat resistance has been proposed, for example, a polymer obtained by polymerizing a monomer component containing maleimide (for example, refer to Japanese Patent Laid-Open Publication No. 2003-201316 a polymer obtained by combining a compound of a specific structure, that is, an ether dimer of 2-(hydroxyalkyl) acrylate (for example, refer to Japanese Patent Laid-Open Publication No. 2〇〇4·3〇〇2 )Wait. ^ However, the case where the polymers are thermally decomposed upon heating in the film or film forming step and the decomposition gas is generated is quite remarkable. For example, when such a polymer is used as a photosensitive resin for producing a liquid crystal display or a printed wiring board, the decomposition product generated during heating in the manufacturing step may contaminate the heating furnace, or the decomposition product may stain the liquid crystal. , the substrate and the electrical insulation is reduced. Further, a maleimide, a hexamethylene, and a polymer having an acid group have been proposed (for example, refer to Japanese Patent Laid-Open Publication No. 2002-301-19). However, such a polymer has a problem that the dissolution rate of the organic compound and the 丨 ra AH is slow. Therefore, it is required to have a polymer, and it is easy to prepare a resin composition while being heat-resistant between the two pieces, and it is possible to improve developability when used as a photosensitive yttrium. [Explanation] 5 200914474 kinds of polymers, which are excellent in heat resistance In order to solve the above problems, the inventors of the present invention have found that it is possible to reduce the gas generated during heating, and to improve the alkali developability. Highly copolymerized with an N-substituted maleimide and/or a compound of a specific structure, ie, a ketone-based acrylic acid ether dimer, a vinyl toluene, and a monomer having an acid group as essential components A molecule (p〇lymer) can solve this problem in one fell swoop, and the present invention is completed in the present invention. That is, the present invention is characterized by being N-substituted maleimide and/or represented by the following formula (1). A polymer obtained by copolymerizing a compound, vinyl toluene, and a monomer having an acid group as an essential component.
(1) (式（1)中’ R1及R2分別獨立，表示氫原子或可具有取 代基之碳數1~25之煙基）。 【實施方式】 本案說明書中之「以上」、「以下」係包含該數値。 亦即’ 「以上」意指不少於（該數値以及該數値以上）。 本發明之聚合物係以N-取代馬來酿亞胺及/或下述通 式（1)所表示之化合物（以下有時稱為「醚二聚物」）、乙烯 基甲笨、以及具有酸基之單體作為必須成分共聚合而成之 聚合物。 200914474 (式（1)中R及R2分別獨立，表示氫原子或可具有取 代基之碳數1〜2 5之烴基。） 藉此使用有本發明聚合物之感光性樹脂組成物成為 而于熱性及透明性皆極為優異者。推測此原因在於因將义取 代馬來醯亞胺、前述醚二聚物加以聚合所形成之主鏈環結 構、以及乙稀基甲苯結構而耐熱性大幅提高且熱分解受到 抑制（耐熱分解性提高）所致。 又’本發明人發現到關於感光性樹脂之財熱性，若聚 合物中有酯鍵結，則容易熱分解。因此，本發明之聚合物 中構方面以貫資上不具有S旨鍵結較佳。此種聚合物， 除了具有環結構之單體以及具有酸基之單體以外，係考慮 將苯乙烯、乙烯基甲苯等不具有酯鍵結的單體加以共聚合 所成者。其中’尤其在解決了上述課題後，發現使用乙烯 基甲本於本技術領域中係達到無法預期之效果，十分優 異。亦即’藉由使用乙烯基曱苯，可形成對於有機溶劑、 驗之溶解速度可提高，且易於調製樹脂組成物，用於作為 感光性樹脂時鹼顯影性優異之硬化塗膜。 以下，說明前述聚合物。 前述N-取代馬來醯亞胺可舉出：N_甲基馬來醯亞胺、 N-異丙基馬來醯亞胺、N-環己基馬來醯亞胺等烷基取代馬 來醯亞胺、N-苯基馬來醯亞胺、N-苄基馬來醯亞胺等具有 芳香族基之馬來醯亞胺。該等之中，由對溶劑之溶解性、 200914474 耐熱分解性、工業上容易取得等觀點央 祝.5采看，較佳為N-苯基 馬來醯亞胺、N-環己基馬來醯亞胺、N # ^ N-下基馬來醯亞胺。 該等之中，由對溶劑之溶解性、加埶睥 ％之者色少之觀點來 看，最佳為N-苄基馬來醯亞胺。 表示前述醚二聚物之前述通式（1)中，R1以及R2所表 不之可具有取代基之碳冑1〜25之烴基並無特別限制，可 舉出例如：甲基、乙基、正丙基、異丙基、正丁基、異丁 基、第三丁基、第三戊基、硬脂醯基、月桂基、2_乙基己 基等直鏈狀或支鏈狀烷基；苯基等芳香基；環己基、第三 丁基環己基、二環戊二烯基、三環癸烯基、異莰基 (is〇b〇rnyl)、金剛烷基（adamantyl)、2_甲基_2_金剛烷基等 脂環式基；以卜甲氧基乙基、卜乙氧基乙基等之烷氧基取 代之烷基；以苄基等芳香基取代之烷基；等。該等之中碳 數較佳為8以下，再者，由耐熱性之觀點來看，較佳為如 甲基、乙基、環己基、苄基、2_乙基己基等這類難以因酸、 熱而脫離之1級或2級碳之取代基。其中，Ri以及R2可 為同種取代基，亦可為不同之取代基。 前述醚二聚物之具體例可舉出例如：二曱基_2,2，-[氧 雙（亞曱基）]雙-2-丙稀酸醋（dimethyUj’-foxybisi^methyleneAis-S-propenoate) 、 二乙基_2,2’-[氧雙 （亞 曱基）]雙-2·•丙烯酸酯、二（正丙基）_2,2，_[氧雙（亞曱基y雙_2_ 丙稀酸i旨、二（異丙基）_2,2，_[氧雙（亞曱基）]雙-2-丙烯酸 醋、二（正丁基）-2,2，-[氧雙（亞甲基雙_2_丙烯酸酯、二（異 丁基）_2,2’-[氧雙（亞甲基）]雙-2·丙烯酸酯、二（第三丁基 8 200914474 2,2’-[氧雙（亞曱基）]雙_2_丙烯酸酯、二（第三戊基）_2,2，-[氧 雙（亞曱基）]雙-2-丙稀酸醋、二（硬脂醯基）_2,2，_[氧雙（亞曱 基）]雙-2-丙烯酸酯、二（月桂基）_2,2，_[氧雙（亞甲基乃雙_2_ 丙烯酸酯、二（2-乙基己基）_2,2，_[氧雙（亞甲基）]雙_2_丙烯 酸酿、二（1-甲氧基乙基）_2,2，_[氧雙（亞甲基）]雙_2·丙烯酸 酯、二（1_乙氧基乙基）_2,2，_[氧雙（亞甲基）]雙_2_丙烯酸酯、 二苄基_2,2’_[氧雙（亞甲基）]雙-2-丙烯酸酯、二苯基_2,2，_[氧 雙（亞曱基）]雙-2-丙烯酸酯、二環己基_2,2、氧雙（亞曱基乃 雙-2-丙烯酸酯、二（第三丁基環己基）_2,2，_[氧雙（亞曱基 雙-2-丙烯酸酯、二（二環戊二烯基）_2,2，_[氧雙（亞曱基乃雙_ 2-丙烯酸酯、二（三環癸烯基）_2,2，_[氧雙（亞甲基）]雙_2_丙 烯酸酯、二（異莰基）_2,2，_[氧雙（亞曱基）]雙_2_丙烯酸酯、 二金剛烷基-2,2’-[氧雙（亞甲基）]雙-2-丙稀酸酯、二曱基 -2-金剛烷基）-2,2’-[氧雙（亞甲基）]雙_2·丙烯酸酯等。 該等之中尤其以=甲基_2,2，_[氧雙（亞曱基）]雙冬丙稀 酸酯、二乙基-2,2，-[氧雙（亞甲基）]雙_2_丙烯酸酯、二環己 基-2,2 -[氧雙（亞甲基）]雙_2_丙烯酸酯、二苄基[氧雙 (亞甲基）]雙-2-丙烯酸酿、二（2_乙基己基）_2,2，_[氧雙（亞甲 基）]雙-2-丙烯酸醋為佳。言亥等醚二聚物可僅為丨種，亦可 為2種以上。 獲得本發明之聚合物時之單體成分中N_取代馬來醯亞 胺及/或前述醚二聚物之比例並無特別限制，但於總單體成 分中為2〜60質量，較佳為5〜5〇質量，更佳為5〜^質=。 N-取代馬來醯亞胺及/或醚二聚物的量若過多 則有對溶 200914474 劑、鹼之溶解性降低、或聚合時會變得容易析出或凝膠化 之虞。另一方面，若過少，則有耐熱性不足之虞。 丽述乙烯基曱笨有鄰乙烯基曱苯、對乙烯基曱苯、間 乙烯基甲苯。該等之中，工業上取得容易之間乙烯基甲苯、 對乙烯基曱苯、以及間乙烯基甲苯與對乙烯基甲苯之混合 物為佳，尤其以工業上取得容易之間乙烯基甲苯與對乙烯 基甲苯之混合物較適合。 f 前述聚合物之單體成分中乙烯基甲苯之比例並無特別 限制，於總單體成分中為5〜80質量％，較佳為1〇〜7〇質量 /〇,更佳為15〜60質量％。乙烯基曱苯的量若過多，則對 鹼之溶解性有降低之虞。又，若過少，則有熱安定性降低 且加熱時分解氣體產生變多之虞。 前述具有酸基之單體（含有酸基之單體）例，只要是具 有酸基與聚合性雙鍵之單體即無特別限制，較佳為丙烯 駄、甲基丙烯酸。尤其，本發明之聚合物因含有乙烯基甲 ( 苯單位作為必須成分故疏水性強。因此，為了發揮充分鹼 可〉谷性，較強親水性之丙稀酸最佳。 别述聚合物之單體成分中含有酸基之單體之比例並無 特另!限制，實質上於總單體成分中為5〜質量％較佳，8〜 貝里0/〇更佳，8〜20質量％最佳。含有酸基之單體量若過少， 則驗可溶性有不足之虞。又，若過多，則耐熱分解性會降 低或對溶劑之溶解性有降低之虞。此處，含有酸基之單體 之實質比例，係指除去為了將反應性雙鍵導入於後述之侧 鍵而使（甲基）丙烯酸縮水甘油酯等反應所消耗之量的比 10 200914474 例。本發明中，如後所述’為了將反應性雙鍵導入於側鏈， 有時會使（甲基）丙烯酸縮水甘油酯等進行反應。此時，所 消耗之含有酸基之單體量必須預先增加至上述量，增加後 的含有酸基之單體總重較佳為15〜60質量％，更佳為2〇〜55 質量％，最佳為20〜50質量％。 本發明之聚合物雖然可含有或不含有上述必須之單體 單位以外的單體單位，但上述必須之單體單位占聚合物之 合計質量比例例如50質量％以上較佳。更較佳為7〇質量 〇/〇以上，再更佳為90質量％以上，而實質上所有的成分皆 為必須之平體單位最佳。 本發明聚合物中之單體單位的排列形態可為例如：無 規共聚物、交替共聚合物、嵌段共聚合物之任一者。 本發明之聚合物進一步於側鏈含有聚合性雙鍵較佳。 藉由於側鏈帶有聚合性雙鍵，可以熱、光來進行硬化。因 此，耐熱分解性更為提高之外，製成感光性樹脂組成物時 對光之感度提南，可以較少的光進行硬化且硬化後機械強 度亦變高。將聚合性雙鍵導入於側鏈之方法較佳為將帶有 與雙鍵及酸基反應之官能基之單體與前述聚合物酸基的局 部反應之方法。帶有與雙鍵及酸基反應之官能基之單體較 佳為（甲基）丙烯酸縮水甘油酯、（甲基）丙烯酸_3,4_環氧基 環己酯、異丙烯基噁唑啉等，從工業取得容易性、反應性 之觀點來看，甲基丙烯酸縮水甘油酯最佳。其中，本說明 書中’「（曱基）丙烯酸」係表示甲基丙烯酸與丙烯酸兩者 之記載。 200914474 將雙鍵導入於側鏈時，就雙鍵之含量而言，雙鍵當量 為萬較佳、彻〜i萬更較，鳩〜删最佳。雙鍵 當量過高時，對光之感度有變低之虞，又，雙鍵當量過低 時，有保存安定性變差或對溶劑之溶解性降低之虞。將（甲 基）丙烯酸縮水甘油自旨等帶有與雙鍵及酸基反應之官能基之 早體加成於聚合物中酸基局部之方法可採用習知方法，並 無特別限制，反應溫度較佳為6〇。〇〜14代，又，使用三乙 月安、二甲基节胺等胺化合物、四乙基氣化録等館鹽、四苯 基〉臭化鱗等鱗鹽、二甲基曱醯胺等酿胺化合物等習知之觸 媒較佳。 前述聚合物係如上所述，較佳為實質上所有的成分皆 為必肩之單體單位，但亦可視需要含有其他可共聚合之單 體。 剷述其他可共聚合之單體可舉出例如：苯乙烯等之芳 香族乙烯基化合物；（甲基）丙烯酸曱酯、（曱基）丙烯酸乙酯、 (甲基）丙烯酸正丙酯、（甲基）丙烯酸異丙酯、（甲基）丙浠酸 正丁酯、（甲基）丙烯酸異丁酯、（曱基）丙烯酸第三丁酯、（甲 基）丙烯酸2-乙基己酯、（甲基）丙烯酸環己酯、（甲基）丙烯 酸TS旨、（曱基）丙烯酸2-羥基乙酯等（甲基）丙烯酸酯類； 丁二烯、異戊二烯等丁二烯或取代丁二烯化合物；乙烯、 丙烯、氯乙烯基、丙稀腈等乙烯或取代乙烯化合物；乙酸 乙烯酯等乙烯酯類；等。該等之中較佳為（曱基）丙烯酸曱 醋、（甲基）丙烯酸環己酯、（曱基）丙烯酸苄酯。該等可共聚 合之其他單體可僅使用1種亦可併用2種以上。其中，本 12 200914474 說明書中 兩者。 (甲基）丙烯酸」係表示甲基丙烯酸與两稀酸 獲得前述聚合物時之單體成分包含前述可共聚合之其 他單體的情況時，其含有比例並無特別限制，較佳為聚人 物中50質量％以下，更佳為3〇質量％以下，再更佳為= 質量％以下。尤其，（甲基）丙烯酸酯類因耐熱安定性差， 故於加熱時易於發生醇從酯結構脫離。因此，（甲基）丙烯 酸_的情況時，較佳為20質量％以下，更佳為夏/質量％ 以下，再更佳為實質上不含（甲基）丙烯酸酯。其中，於^甲0 基）丙烯酸單位加成有（曱基）丙稀酸縮水甘油S旨等單位因加 熱時會交聯，故熱安定性降低少。本發明中，（甲基）丙烯 酸醋並不含有於（甲基）丙㈣單位加成有（曱基）㈣水 甘油酯之單位。 〜 月_J述單體成分之聚人Θ處 乂刀；承σ反應方法並無特別限制， :往習知的各種聚合方法，但以溶液聚合法進行尤佳。： ::單聚::度、聚合濃度(聚合濃度(%)=[翠體成分之總重 成刀之總重量+溶劑重量）]侧）雖因所使用之單體 :刀的種類或比率、目標高分子之分子量而異，作定2 〜皿度40〜15(rc、聚合濃度2〇〜5 60〜13代、聚合W45%更佳。 疋為皿度 由基體成分之聚合中使用溶劑時，使用-般的自 舉出例：使用之溶劑做為溶劑即可。具體而言，可 四氫咳喃…惡貌、乙二醇二甲基趟、二乙： 甲基物類；丙酮、甲乙嗣、甲基異丁酮、環己： 13 200914474 專酉同類；乙酸乙酉旨、乙酸丁醋、丙二醇單甲基趟乙酸醋、 乙酸3^甲氧基丁^旨等^旨類；甲醇、乙醇、異丙醇、正丁醇、 乙二醇單甲基蜮、丙二醇單甲基趟等醇類；甲苯、二甲苯、 乙基苯等芳香族煙類；氯仿；二曱基亞硬；等。該等溶劑 可僅使用1種或併用2種以上。X，尤其在含有酸基之單 體含量超過30質量％的情況時’為了防止重量體的析出， 較佳為丙二醇單甲基喊乙酸S旨等S旨系溶劑與、丙二醇單甲 基謎、異丙醇等醇系溶劑之混合溶劑。其中，此處之含有 酸基之單體的含量係指增加了為了於側鏈導入反應性雙鍵 所消耗之量。 將前述單體成分加以聚合時，視需要亦可添加—般使 用之：合起始劑。聚合起始劑並無特別限制’可舉出例如： 異=苯過氧化氫（eumene hydrGpe⑽也）、：異丙基苯過氧 化虱過乳化一-第三丁基、過氧化月桂醯、過氧化苯甲醯、 過氧化第三丁基異丙基碳㈣、過氧2•乙基己酸第 醋、過氧-2-乙基己酸第三丁醋等有機過氧化物；2,2， 雙（.異丁腈）、U，·偶氮雙（環己曱腈）（U，· az〇b1S(cyclohexanecarb〇nitrile))、2,2，_ 偶 i 雙（2，二甲 =戊腈）、二甲基2,2、偶氣雙（2·甲基丙酸等偶氣化合 物％玄專聚合起始劑可僅使用！種或併用2種以上。其中 起=劑之使用量可因應所使用之單體的組合、反應⑽; 子之分子量等來適當地設定，並無特別限定，作 攸可獲得不會凝膠化且重量平均分子量為數千〜數萬之古 分子之觀點來看，相對於總單體成分為〇 ι〜ΐ5質量％，： 14 200914474 佳為〇_5〜ι〇質量％。 I別述早體成分加以聚合時，為了調整分子量，亦可 如=添加-般所使用之鏈轉移劑。鏈轉移劑可舉出例 -说基硫酵（n_dodecyi赠叫叫、織基丙酸、魏 基乙酸甲酯等硫醇系鏈轉移劑、Η基苯乙稀 ^物# ’但以鏈轉移效果高且可減少殘存單體、取得容 正：二院基硫醇、疏基丙酸較佳。使用鏈轉移劑的情 目^ 量可因應所使狀單體的組合、反應條件、 *间分子之分子量等適當地設定，無特別限定，但從可 獲得不會凝膠化且重量平均分子量為數千〜數萬之高分子 之觀點來看’較佳為相對於總單體成分為〜〗5質量％， 更佳為0 · 5〜1 0質量％。 i本發明之聚合物之重量平均分子量雖無特別限制，但 較佳為2000〜200000、更佳為5〇〇〇〜1〇〇〇〇〇。重量平均分 子2超過200000時，會變得過高黏度而難以形成塗膜， 另—方面’若未滿2GGG，則有變得難以展現充分财熱性的 傾向。其中’ ^量平均分子量之測定方法係示於下述實施 例。 月J述聚5物，酸>f貝為30〜3〇〇mgK〇H/g較佳，更佳為 50 20〇mgK〇H。酸價未滿3〇mgK〇H/g時，則難以適用於 鹼顯影；超過300mgK〇H/g時，則會變得過高黏度而有難 '开/成塗膜之傾向。又，對於溶劑之溶解性會變低，於合 成中析出，有無法攪拌之虞。 本發明之聚合物雖可特別適用於作為熱硬化性樹脂組 15 200914474 成，感光性樹脂組成物之黏結劑高分子，但以作為感光 性樹舳組成物之黏結劑特佳。用作為感光性樹脂組成物之 黏結劑打，前述聚合物之外，配合自由基聚合性化合物、 光聚合起始劑，溶劑之外，視需要配合增感劑、顏料、顏 料分散劑、界面活性劑等較佳。 光聚合起始劑可舉出：2_氯噻噸酮等噻噸酮類；苯乙 酮二甲基縮酮、节基二甲基縮酮等縮酮類；二苯基酮等二 苯基酮類；2-甲基-1-[4-(曱基硫）苯基]_2_嗎啉基_丙_丨_酮、 2-苄基-2-二甲基胺基-i_(4_嗎啉基苯基）_ 丁酮_丨；醯基膦氧 化物（acylphosphine 0Xide)類以及氧雜蔥酮（xanth〇ne)類 等’該等可單獨使用亦可併用2種類以上。 又其含有比例相對於前述聚合物，較佳為〇1〜5〇質 量％，更佳為0.5〜30質量％。 本發明之聚合物，視需要可含有作為稀釋劑之溶劑。 前述溶劑只要是將聚合物均勻溶解且不會反應者即不特別 限制。具體而言可舉出例如：四氫吱喃、二„惡烧、乙_ ^ 一甲基趟、二乙一醇二甲基謎等喊類；丙酮、曱乙綱、甲 基異丁基酮、環己烷等酮類；乙酸乙酯、乙酸丁醋、肉_ 醇單甲基醚乙酸酯、乙酸3-曱氧基丁酯等酯類；甲醇、Z 醇、異丙醇、正丁醇、乙二醇單甲基趟、丙二醇單曱茂鍵 等醇類；曱苯、二甲苯、乙基苯等芳香族烴類；氣仿 曱基亞碾；等。其中，溶劑之含量可因應使用時之最適黏 度適當地設定。 本發明之聚合物係耐熱性高且加熱時之分解氣體小 16 200914474 人 °』形成極優異之塗膜，且對於. ^ 、有機溶劑、鹼之溶 T，故可適用於例如感光性樹脂組成物、各種塗 佈劑、塗料等用途。(1) (In the formula (1), R1 and R2 are each independently, and represent a hydrogen atom or a ketone group having a carbon number of 1 to 25 which may have a substituent. [Embodiment] The "above" and "below" in the present specification include the number. That is, 'above' means not less than (the number and the number). The polymer of the present invention is an N-substituted maleimide and/or a compound represented by the following formula (1) (hereinafter sometimes referred to as "ether dimer"), a vinyl group, and A polymer in which an acid group monomer is copolymerized as an essential component. 200914474 (wherein R and R2 in the formula (1) are each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.) The photosensitive resin composition having the polymer of the present invention is used as the heat. And the transparency is extremely excellent. It is presumed that the reason is that the heat resistance is greatly improved and the thermal decomposition is suppressed (heat decomposition resistance is improved by the main chain ring structure formed by polymerization of the substituted maleimide and the ether dimer, and the ethylbenzene toluene structure. ) caused. Further, the inventors have found that the heat resistance of the photosensitive resin is likely to be thermally decomposed if there is an ester bond in the polymer. Therefore, it is preferred that the polymer of the present invention has a structurally unsupported bond. Such a polymer is preferably a copolymer of a monomer having no ester bond, such as styrene or vinyltoluene, in addition to a monomer having a ring structure and a monomer having an acid group. Among them, in particular, after solving the above problems, it has been found that the use of vinyl based on the present invention achieves an unexpected effect, which is very advantageous. In other words, by using vinyl benzene, it is possible to form a cured coating film which is improved in the dissolution rate with respect to an organic solvent and which is easy to prepare a resin composition, and which is excellent in alkali developability as a photosensitive resin. Hereinafter, the above polymer will be described. The N-substituted maleimide may be an alkyl-substituted maleate such as N-methylmaleimide, N-isopropylmaleimide or N-cyclohexylmaleimide. An aromatic group-containing maleimide such as an imine, N-phenylmaleimide or N-benzylmaleimide. Among these, from the viewpoints of solubility in a solvent, heat-decomposability in 200914474, and industrially easy to obtain, it is preferable to look at N-phenylmaleimide and N-cyclohexylmalan. Imine, N # ^ N- lower base maleimide. Among these, from the viewpoint of solubility in a solvent and a small color increase, N-benzylmaleimide is preferred. In the above-mentioned general formula (1) of the ether dimer, the hydrocarbon group of the carbonium 1 to 25 which may have a substituent represented by R1 and R2 is not particularly limited, and examples thereof include a methyl group and an ethyl group. a linear or branched alkyl group such as n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, third pentyl, stearyl sulfhydryl, lauryl or 2-ethylhexyl; An aromatic group such as phenyl; cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecenyl, is〇b〇rnyl, adamantyl, 2_A An alicyclic group such as a 2-adamantyl group; an alkyl group substituted with an alkoxy group such as a methoxyethyl group or an ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group; The carbon number in these is preferably 8 or less. Further, from the viewpoint of heat resistance, it is preferably such as a methyl group, an ethyl group, a cyclohexyl group, a benzyl group or a 2-ethylhexyl group. a substituent of the first or second order carbon that is thermally removed. Wherein Ri and R2 may be the same substituent or different substituents. Specific examples of the ether dimer include, for example, dimercapto-2,2,-[oxybis(indenyl)]bis-2-propionic acid vinegar (dimethyUj'-foxybisi^methyleneAis-S-propenoate , diethyl 2,2'-[oxybis(indenyl)]bis-2·•acrylate, di(n-propyl)_2,2,_[oxybis(indenyl y-double_2_) Acrylic acid, di(isopropyl)_2,2,_[oxybis(indenyl)]bis-2-propenoic acid vinegar, di(n-butyl)-2,2,-[oxybis(Asian) Methyl bis- 2 acrylate, di(isobutyl) 2,2'-[oxybis(methylene)]bis-2·acrylate, di(t-butyl 8 200914474 2,2'-[ Oxygen bis(indenyl)]bis_2_acrylate, bis(third amyl)_2,2,-[oxybis(indenyl)]bis-2-propionic acid vinegar, di(stearate) Base)_2,2,_[oxybis(indenyl)]bis-2-acrylate, bis(lauryl)_2,2,_[oxybis(methylenebis-2_acrylate, bis(2) -ethylhexyl)_2,2,_[oxybis(methylene)]bis_2_acrylic acid, bis(1-methoxyethyl)_2,2,_[oxybis(methylene)] Double_2·acrylate, bis(1-ethoxyethyl)_2,2,_[ Bis(methylene)]bis_2_acrylate, dibenzyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diphenyl-2,2,_[oxygen Bis(indenyl)]bis-2-acrylate, dicyclohexyl-2,2, oxybis(indenyl bis-2-acrylate, bis(t-butylcyclohexyl)_2,2,_ [Oxygen bis(indenyl bis-2-acrylate, bis(dicyclopentadienyl)_2,2,_[oxybis(indenyl bis- 2-acrylate, bis(tricyclodecenyl) _2,2,_[oxybis(methylene)]bis_2_acrylate, bis(isoindenyl)_2,2,_[oxybis(indenyl)]di_2_acrylate, two Adamantyl-2,2'-[oxybis(methylene)]bis-2-propionic acid ester, dimercapto-2-adamantyl)-2,2'-[oxybis(methylene) )] double_2·acrylate, etc. Among these, especially = methyl-2,2,_[oxybis(indenyl)]-m-butyl acrylate, diethyl-2,2,- [oxybis(methylene)]bis_2_acrylate, dicyclohexyl-2,2-[oxybis(methylene)]bis_2_acrylate, dibenzyl[oxybis(methylene) )] bis-2-acrylic acid, bis(2-ethylhexyl)_2,2,_[oxybis(methylene)] -2-Acrylic acid vinegar is preferred. The ether dimer such as Yanhai may be only lanthanum or two or more. N_substituted maleimide and/or in the monomer component when the polymer of the present invention is obtained The ratio of the ether dimer is not particularly limited, but is 2 to 60 mass, preferably 5 to 5 Å, more preferably 5 to 5 in the total monomer component. If the amount of the N-substituted maleimide and/or the ether dimer is too large, the solubility in the solvent of 200914474, the alkali may be lowered, or the polymerization may be easily precipitated or gelled. On the other hand, if it is too small, there is a lack of heat resistance. Lithium vinyl is stupid with o-vinyl benzene, p-vinyl benzene, and methylene toluene. Among these, it is industrially easy to obtain a mixture of vinyl toluene, p-vinyl fluorene, and a mixture of m-vinyl toluene and p-vinyl toluene, especially industrially easy to obtain between vinyl toluene and ethylene. A mixture of toluene is preferred. f The ratio of vinyl toluene in the monomer component of the above polymer is not particularly limited, and is 5 to 80% by mass, preferably 1 to 7 〇 mass/〇, more preferably 15 to 60 in the total monomer component. quality%. If the amount of vinyl benzene is too large, the solubility of the alkali is lowered. Further, if the amount is too small, the thermal stability is lowered and the decomposition gas is increased during heating. The monomer having an acid group (the acid group-containing monomer) is not particularly limited as long as it is a monomer having an acid group and a polymerizable double bond, and is preferably propylene or methacrylic acid. In particular, since the polymer of the present invention contains a vinyl group (the benzene unit is an essential component, it has a high hydrophobicity. Therefore, in order to exhibit sufficient alkali, it is preferable to be a glutamic acid, and a more hydrophilic acrylic acid is preferred. The ratio of the monomer having an acid group in the monomer component is not particularly limited; it is preferably 5 to 9% by mass in the total monomer component, more preferably 8 to Berry 0/〇, and 8 to 20% by mass. If the amount of the monomer having an acid group is too small, the solubility is insufficient. Further, if it is too large, the thermal decomposition resistance is lowered or the solubility of the solvent is lowered. Here, the acid group is contained. The substantial ratio of the monomer refers to the ratio of the amount of the amount of the reaction which is used to introduce a reactive double bond into the side bond described later to reduce the amount of the reaction such as glycidyl (meth)acrylate. In the present invention, as in the following, In order to introduce a reactive double bond into a side chain, a reaction of glycidyl (meth)acrylate or the like may be carried out. At this time, the amount of the acid group-containing monomer to be consumed must be increased to the above amount in advance, and increased. The total weight of the latter acid group-containing monomer is preferably 1 5 to 60% by mass, more preferably 2 to 55% by mass, most preferably 20 to 50% by mass. The polymer of the present invention may or may not contain a monomer unit other than the above-mentioned necessary monomer unit, but the above The ratio of the monomer unit to the total mass of the polymer is preferably 50% by mass or more, more preferably 7 〇 〇 / 〇 or more, still more preferably 90% by mass or more, and substantially all of the components are necessary. The flat unit is optimal. The arrangement of the monomer units in the polymer of the present invention may be, for example, any of a random copolymer, an alternating copolymer, and a block copolymer. The polymer of the present invention is further It is preferable that the side chain contains a polymerizable double bond. Since the side chain has a polymerizable double bond, it can be hardened by heat or light. Therefore, the heat-resistant decomposability is further improved, and the light-sensitive resin composition is used as a light-sensitive resin composition. The sensitivity of the south is hardened by less light and the mechanical strength is also higher after hardening. The method of introducing the polymerizable double bond into the side chain is preferably a single one having a functional group reactive with a double bond and an acid group. Body with the aforementioned polymer acid group The method of the partial reaction. The monomer having a functional group reactive with a double bond and an acid group is preferably glycidyl (meth)acrylate, _3,4-epoxycyclohexyl (meth)acrylate, or different. Acrylic oxazoline or the like is preferred from the viewpoint of easiness and reactivity in the industry. In the present specification, '((fluorenyl)acrylic acid) means methacrylic acid and acrylic acid. 200914474 When the double bond is introduced into the side chain, the double bond equivalent is preferably 10,000, more than 10,000, and 删~ is optimal. When the double bond is too high, When the sensitivity to light is lowered, when the double bond equivalent is too low, the stability of storage stability is deteriorated or the solubility of the solvent is lowered. The glycidyl (meth)acrylate has a double The method of adding the bond and the acid group-reactive functional group to the acid group in the polymer can be carried out by a conventional method, and is not particularly limited, and the reaction temperature is preferably 6 Å. 〇~14 generations, and the use of amine compounds such as triethylene sulphate and dimethyl sulphate, tetraethyl sulphate, etc., tetraphenyl sulphate scales and other scale salts, dimethyl decylamine, etc. A known catalyst such as a brewing amine compound is preferred. The above polymers are as described above, and it is preferred that substantially all of the components are monomer units of the shoulder, but other copolymerizable monomers may be contained as needed. Examples of other copolymerizable monomers include aromatic vinyl compounds such as styrene; decyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate; Isopropyl methacrylate, n-butyl (meth)propionate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylates such as (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid TS, (hydroxy)acrylic acid 2-hydroxyethyl ester, etc.; butadiene or substituted such as butadiene or isoprene Butadiene compound; ethylene or substituted ethylene compound such as ethylene, propylene, vinyl chloride or acrylonitrile; vinyl ester such as vinyl acetate; Among these, preferred are (mercapto)acrylic acid vinegar, (meth)acrylic acid cyclohexyl ester, and (mercapto)acrylic acid benzyl ester. These other monomers which can be copolymerized may be used alone or in combination of two or more. Among them, the two of the 12 200914474 instructions. (Meth)acrylic acid means that when the monomer component when the methacrylic acid and the dilute acid obtain the polymer contain the other monomer copolymerizable, the content ratio is not particularly limited, and it is preferably a poly capita. The content is 50% by mass or less, more preferably 3% by mass or less, and even more preferably 5% by mass or less. In particular, since (meth) acrylates are inferior in heat stability, the alcohol is apt to be detached from the ester structure upon heating. Therefore, in the case of (meth)acrylic acid _, it is preferably 20% by mass or less, more preferably Xia/% by mass or less, and still more preferably substantially no (meth) acrylate. Among them, the unit is added to the unit of acrylonitrile, and the unit of the thioglycolic acid glycidyl group is crosslinked by heating, so that the thermal stability is less reduced. In the present invention, (meth)acrylic acid vinegar is not contained in units of (meth)propan (tetra) unit-added (fluorenyl)(tetra)hydroglyceride. ～ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ : :: Monomer:: Degree, polymerization concentration (polymerization concentration (%) = [total weight of the total weight of the sapphire component + solvent weight)] side) Although the monomer used: the type or ratio of the knife The molecular weight of the target polymer varies, and it is determined to be 2 to 40 degrees F1 (rc, polymerization concentration 2〇~5 60~13 generation, and polymerization W45% is better. 疋 is the solvent used in the polymerization of the matrix component. When using the general bootstrap example: the solvent used can be used as a solvent. Specifically, it can be tetrahydrocure...formation, ethylene glycol dimethyl hydrazine, diethylene: methyl species; acetone , methyl ethyl hydrazine, methyl isobutyl ketone, cyclohexyl: 13 200914474 specializes in the same kind; acetic acid ethyl acetate, acetic acid butyl vinegar, propylene glycol monomethyl hydrazine acetate, acetic acid 3 methoxy butyl hydrazine, etc.; methanol , alcohols such as ethanol, isopropanol, n-butanol, ethylene glycol monomethylhydrazine, propylene glycol monomethylhydrazine; aromatic tobaccos such as toluene, xylene, ethylbenzene; chloroform; dimercapto; The solvent may be used alone or in combination of two or more. X, especially when the content of the monomer having an acid group exceeds 30% by mass, in order to prevent The precipitation of the weight is preferably a mixed solvent of a solvent such as propylene glycol monomethyl ketone acetic acid S, an alcohol solvent such as propylene glycol monomethyl mystery or isopropyl alcohol, wherein the acid group is contained therein. The content of the body means an amount which is increased in order to introduce a reactive double bond to the side chain. When the monomer component is polymerized, it may be added as usual: a starting initiator. There is no particular limitation 'for example: iso-benzene hydroperoxide (eumene hydrGpe (10) also), cumene ruthenium peroxide over-emulsified mono-t-butyl, oxidized laurel, benzammonium peroxide, Oxidized tert-butyl isopropyl carbon (tetra), peroxy-2-ethylhexanoic acid vinegar, peroxy-2-ethylhexanoic acid third butyl vinegar and other organic peroxides; 2, 2, double (. Nitrile), U, azobis(cyclohexanecarbonitrile), 2,2,_ even ibis (2, dimethyl = valeronitrile), dimethyl 2, 2, dioxin bis (2 · methyl propionic acid and other odor compounds % Xuan special polymerization initiator can be used only! or two or more kinds of use. It can be suitably set according to the combination of the monomers to be used, the reaction (10), the molecular weight of the substrate, etc., and is not particularly limited, and it is possible to obtain an ancient molecule which does not gel and has a weight average molecular weight of several thousands to several tens of thousands. In view of the above, the total monomer component is 〇ι~ΐ5 mass%, and: 14 200914474 is preferably 〇5~ι〇 mass%. I, when the early components are polymerized, in order to adjust the molecular weight, Adding a chain transfer agent used in general - a chain transfer agent can be exemplified by a thiol-based chain transfer agent such as n-dodecyi, woven propionic acid, methyl thioglycolate, and mercapto phenylene Rare ^物# 'But the chain transfer effect is high and the residual monomer can be reduced, and the positive volume can be obtained: the second-base thiol and the sulfo-propionic acid are preferred. The amount of the chain transfer agent to be used may be appropriately determined depending on the combination of the monomer to be used, the reaction conditions, the molecular weight of the molecule, and the like, and is not particularly limited, but the gelation is not obtained and the weight average molecular weight is The viewpoint of the polymer of thousands to tens of thousands is preferably 5% by mass with respect to the total monomer component, more preferably 0. 5 to 10% by mass. The weight average molecular weight of the polymer of the present invention is not particularly limited, but is preferably from 2,000 to 200,000, more preferably from 5 to 1 Torr. When the weight average molecular weight 2 exceeds 200,000, the viscosity is too high and it is difficult to form a coating film. On the other hand, if it is less than 2 GGG, it tends to be difficult to exhibit sufficient heat retention. The method for measuring the average molecular weight is shown in the following examples. It is preferable that the acid > f shell is 30 to 3 〇〇 mg K 〇 H / g, more preferably 50 20 〇 mg K 〇 H. When the acid value is less than 3 〇 mg K 〇 H / g, it is difficult to apply to alkali development; when it exceeds 300 mg K 〇 H / g, it tends to be too high in viscosity and it is difficult to open / form a coating film. Further, the solubility in the solvent is lowered, and it is precipitated during the synthesis, and there is a possibility that the solvent cannot be stirred. The polymer of the present invention is particularly suitable as a binder polymer which is a thermosetting resin group 15 200914474, and is preferably a binder of a photosensitive tree composition. It is used as a binder for a photosensitive resin composition, in addition to the above-mentioned polymer, a radical polymerizable compound, a photopolymerization initiator, and a solvent, and a sensitizer, a pigment, a pigment dispersant, and an interfacial activity are optionally added. Agents and the like are preferred. Examples of the photopolymerization initiator include thioxanthones such as 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl ketal; and diphenyl groups such as diphenyl ketone. Ketones; 2-methyl-1-[4-(indolylthio)phenyl]_2-morpholinyl-propanyl- ketone, 2-benzyl-2-dimethylamino-i_(4_ Morpholinylphenyl)-butanone-oxime; acylphosphine 0Xide and xanthene, etc. These may be used alone or in combination of two or more. Further, the content thereof is preferably 〇1 to 5 〇% by mass, more preferably 0.5 to 30% by mass based on the above polymer. The polymer of the present invention may contain a solvent as a diluent as needed. The solvent is not particularly limited as long as it dissolves the polymer uniformly and does not react. Specifically, for example, tetrahydrofuran, dioxin, _^-methyl hydrazine, diethyl diol dimethyl mystery, and the like; acetone, acetonide, methyl isobutyl ketone, Ketones such as cyclohexane; esters such as ethyl acetate, butyl acetate, meat monomethyl ether acetate, 3-methoxybutyl acetate; methanol, Z alcohol, isopropanol, n-butanol Alcohols such as ethylene glycol monomethylhydrazine and propylene glycol monoterpene linkage; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; gas-like fluorenyl amide; etc., wherein the solvent content can be used accordingly The optimum viscosity is set appropriately. The polymer of the present invention has high heat resistance and a small decomposition gas during heating. It can be suitably used for applications, such as a photosensitive resin composition, various coating agents, and coating materials.
:::，藉由實施例詳細說明本發明，但本發明之範圍 ^ rttfV貫施例j除非特別限定，U …刀」。以下之實施例中’各種物性等係用以下方 式測定。 <重量平均分子量> :聚笨乙稀作為標準物質’並以ΤΜ(四氫咬喃)作為 ^液’以HLC_8220GPC(東曹公司製）敎重量平均分子 量° <酸價> 精確枰量樹脂料3g，並溶解於丙綱7〇g/水心混合 溶劑，以瑞香草龄藍（thymol blue)作為指示劑，以〇」N k〇h 水溶液滴定，並由固體成分之濃度求出固體成分每“之 實施例 實施例1 〜j刀雕現瓶加入丙二醇單 甲基醚乙酸酯（PGMEA)IOO重量份，备％ a ^ 至里切’氮取代之後，升溫至9〇 °C。另一方面’於滴下槽！將— 了一 基·2,2’-[乳雙（亞甲基 雙）]-2-丙烯酸酯20_0份、丙烯酸？ 产 ⑼吸25.〇份、過氧-2-乙基己 酸第三丁醋2.0份、PGMEA80份加以混合。又，於滴下槽 2將乙烤基甲苯（間-乙烯基甲苯以及對.乙稀基甲苯為6。比 17 200914474The invention is described in detail by way of examples, but the scope of the invention is rttfV, unless otherwise specified, U. In the following examples, various physical properties and the like were measured by the following formula. <Weight average molecular weight>: Polystyrene is used as a standard substance', and ΤΜ(tetrahydroanthracene) is used as a liquid to be HLC_8220GPC (manufactured by Tosoh Corporation) 敎 weight average molecular weight ° <acid value> The resin material was 3 g and dissolved in a mixed solvent of propylene 7 〇g/water core, and thymol blue was used as an indicator, titrated with an aqueous solution of 〇Nk〇h, and determined from the concentration of solid components. The solid content was added to propylene glycol monomethyl ether acetate (PGMEA) 100 parts by weight per Example Example 1 to j, and the temperature was raised to 9 ° C after the % a ^ to the Liche 'nitrogen substitution. On the other hand, 'drop the trough! Will — a base · 2, 2 '- [milk (methylene bis)]-2-acrylate 20_0 parts, acrylic acid production (9) absorb 25. 〇, peroxy 2.0 parts of 2-ethylhexanoic acid butyl vinegar and 80 parts of PGMEA were mixed. Further, in the dropping tank 2, ethyl bromide toluene (m-vinyltoluene and p-ethylbenzene toluene was 6. Ratio 17 200914474)
40之混合物）55份、正十二基硫酵2.0份加以混合。一邊 將反應溫度保持於9 0 C ’ 一邊以4.0小時從滴下槽1及2 以等速度滴下至反應槽。滴下結束後，保持於9(rc 3〇分鐘 後’投入過氧-2-乙基己酸第三丁酯0.5份，再於90°C繼續 反應30分鐘。之後，將反應溫度升溫至U5t，繼續反應 1 ·5小時。一旦冷卻至室溫後，投入曱基丙烯酸縮水甘油 酉曰19.7份、6 -第三丁基-2,4 -二甲苯盼〇.1〇份、三乙胺〇.3〇 份’並將氧濃度調整至7%之氮、空氣混合氣體加以起泡 同時升溫至11 (TC，並進行反應2小時。之後，升溫至i丨5〇c 並使其反應5小時，再使反應結束，然後冷卻至室溫，择 得聚合物溶液1。 針對所得之聚合物溶液1測定各種物性，以標準物質 為？κ本乙稀之GPC(凝膠滲透層析）所測得之重量平均分子 量為16000,真空下以160。(：乾燥所得之固體成分濃度為 38.1% ’由滴定法所求得之單位固體成分之酸價為 100mgKOH/g。 將100重量份之聚合物溶液1、3〇重量份之二季戊四 醇五丙烯酸酯、3重量之作為光聚合起始劑之伊魯加居亞 907(ciba-geigy公司製）、500重量份之PGMEA加以混合後， 旋塗於玻璃基板上’於9(TC乾燥3分鐘，形成膜厚3 之塗膜1。 將塗膜1在2〇。(：浸潰於PGMEA，以目葙齙资时 M目視觀察膜到完 全溶解為止之時間’到膜溶解為止之時問盔 了「]局15秒。以高 壓水銀燈使塗膜1進行300mJ/cm2之UV日R止 V曝先，再於200。〇 18 200914474 加熱30分鐘，使硬化結束。削下所得之硬化膜，以TG-DTA 法（熱重量-示差熱分析法）所測定之以230°C保持30分鐘時 之重量減少率為1.1 %。所得之測定結果等示於表1。下述 表1係表示實施例1〜3、比較例1〜3之聚合物成分之組成、 聚合物溶液、塗膜、以及硬化膜之物性。 f ί 19 200914474 ss τη 0.5Ϊ—η 8_Α寸 ods oe 08 9.卜ε oil ΓΙA mixture of 40), 55 parts, and 2.0 parts of n-dodecyl thiolate were mixed. While maintaining the reaction temperature at 90 ° C, the mixture was dropped from the dropping tanks 1 and 2 at a constant rate to the reaction vessel at 4.0 hours. After the completion of the dropwise addition, 0.5 part of peroxy-2-ethylhexanoic acid tert-butyl ester was kept at 9 (rc 3 〇 minutes, and the reaction was further continued at 90 ° C for 30 minutes. Thereafter, the reaction temperature was raised to U5t, The reaction was continued for 1.5 hours. Once cooled to room temperature, 19.7 parts of glycidyl hydrazide, 6-t-butyl-2,4-xylene, 1 part by weight, and triethylamine oxime were charged. 3 parts 'The nitrogen and air mixed gas whose oxygen concentration was adjusted to 7% were foamed while raising the temperature to 11 (TC, and the reaction was carried out for 2 hours. Thereafter, the temperature was raised to i丨5〇c and allowed to react for 5 hours. The reaction was completed, and then cooled to room temperature to obtain a polymer solution 1. Various physical properties were determined for the obtained polymer solution 1, and the standard substance was measured by GPC (gel permeation chromatography) of ? The weight average molecular weight is 16,000, and the vacuum is 160. (The solid content concentration obtained by drying is 38.1%' The acid value per unit solid content determined by the titration method is 100 mgKOH/g. 100 parts by weight of the polymer solution 1, 3 parts by weight of pentaerythritol pentaacrylate, 3 parts by weight as a photopolymerization initiator Irujiajuya 907 (manufactured by Ciba-geigy Co., Ltd.) and 500 parts by weight of PGMEA were mixed and spin-coated on a glass substrate at 9 (TC was dried for 3 minutes to form a coating film 1 having a film thickness of 3. The film 1 was placed at 2 〇. (: immersed in PGMEA, and the time until the film was observed to be completely dissolved by the eyesight M) until the film was dissolved, and the mask was applied for 15 seconds. The coating was performed with a high pressure mercury lamp. Film 1 was subjected to a UV-R-V exposure of 300 mJ/cm2, and then heated at 200. 〇18 200914474 for 30 minutes to complete the hardening. The obtained cured film was cut by TG-DTA method (thermogravimetry-differential thermal analysis) The weight loss rate at the time of holding at 230 ° C for 30 minutes was 1.1%. The measurement results obtained and the like are shown in Table 1. Table 1 below shows the polymers of Examples 1 to 3 and Comparative Examples 1 to 3. The composition of the composition, the polymer solution, the coating film, and the physical properties of the cured film. f ί 19 200914474 ss τη 0.5Ϊ—η 8_Α inch ods oe 08 9. Bu ε oil ΓΙ
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Isy潜装肊_®-蚪»-蝴爱to 鍥咄谱馁啤砩驴-N #fi4-=*f 遛谀>«壊镏裝^砩®- as (s/HO:sss^翹 ¥ 屮令 φίτ1Γ¥« (％)资，^\^®w« (，# ornSE^^蘧)倒斂 (，# otNsa赀磙蹑)喇傲 (#οεΪΕ赍轮蘧)銎茏雠B is^i0 $ i $ si 200914474 實施例2 如表1所不’使用N-苄基馬來醯亞胺取代二甲基_ 2,2 -[氧雙（亞甲基雙）]_2_丙烯酸醋，除此之外，係以與實 她例1相同之操作進行來製作塗膜以及硬化膜，並測定物 性等。 塗膜溶解於PGMEA之時間為14秒。 又，硬化膜在230°C、30分鐘之重量減少率為〇 6%。 實施例3 於作為反應槽之附冷卻管之可分離燒瓶加入丙二醇單 甲基醚乙酸酯（PGMEA)100重量份、丙二醇單甲基醚 (PGME)50份，氮取代後，升溫至9〇。〇。另一方面，於滴 下槽1將N-苄基馬來醯亞胺15 〇份、丙烯酸37 2份、過 氧-2-乙基己酸第三丁酯2·〇份、pGMEA56份、pGME24份 加以混合。又，於滴下槽2將乙烯基甲苯（間-乙烯基甲苯 以及對-乙烯基曱苯為60比4〇之混合物）47 8份、正十二 基硫醇3.0份加以混合。一邊將反應溫度保持於9〇。〇，一 邊一邊以4.0小時從滴下槽丨及2以等速度滴下至反應槽。 滴下結束後，保持於90°C 30分鐘後，投入過氧_2_乙基己 酸第三丁醋0.5份，再於90°C繼續反應30分鐘。之後，將 反應溫度升溫至11 5 °C，繼續反應1 ·5小時。一旦冷卻至 室溫後，投入甲基丙烯酸縮水甘油酯50·〇份、6_第三丁基 -2,4 -二曱本盼〇.1〇份、三乙胺〇_30份，並將氧濃度調整 至7%之氮、空氣混合氣體加以起泡同時升溫至n，並 進行反應16小時，以與實施例1相同之方式使反應結束， 21 200914474 然後冷卻至室溫，獲得聚合物溶液。 所得之聚合物溶液之重量平均分子量為13〇〇〇，固體 成分濃度為36.1%，單位固體成分之酸價為8〇mgK〇H/g。 進行與實施例1相同之調配，形成塗膜，到臈溶解於pgmea 為止之時間為16秒。 又’硬化膜以TG-DTA法所測定之以23〇°C保持30分 鐘時之重量減少率為〇.6〇/0。 又，以uv曝光裝置（Topcon公司製TME_150RNS)， 透過線寬15/zm之線與間隔光罩⑴⑽& space mask)，將 塗膜曝光50mJ/cm2之Uv光，並於9〇。〇乾燥3分鐘後，用 史賓顯影機（actes公司製ADE_3〇〇〇s)，以〇 〇1之k〇h水 /合液進行20秒顯影。圖】係表示將曝光後之塗膜鹼顯影 後之玻璃基板狀態。 圖1中，位於上部之格子狀部分（矩形圖案）為透過光 罩所曝光之曝光部，其周圍為光罩所保護之未曝光部。如 圖1所示，於曝光部因塗膜硬化而形成有完整之圖案’未 曝光部則塗膜溶解，確認不到溶解剩下之殘渣。 又，即使將和上述相同之步驟中顯影時間定為30秒來 進行’亦沒有圖案缺陷。 比較例1 士表1所示’使用甲基丙稀酸苄酯取代乙稀基甲苯， 除此之外，係進行與實施例丨相同之操作。塗膜之溶解時 間為10秒，於23〇t，30分鐘之重量減少率為35%。 比較例2 22 200914474 如表1所示’使用苯乙烯取代乙烯基甲苯，除此之外 係進行與實施例1相同之操作。塗膜之溶解時間為24争丨、 較實施例1慢。又，於230°c，加熱30分鐘之重量減少率 為 1.4% 〇 比較例3 如表1所示，使用苯乙烯取代乙烯基曱苯，除此之外 係進行與實施例3相同之操作。塗膜溶解至PGMEA >々 <溶 解時間為30秒，較實施例3長。 硬化膜在230C保持30分鐘之重量減少率為1 1%。 與實施例3相同之條件下進行鹼顯影。圖2係表示將 曝光後之塗膜鹼顯影後之玻璃基板狀態，係與圖1相同， 形成了曝光部與未曝光部。如圖2所示，曝光部雖形成有 圖案。未曝光部則塗膜溶解不完，而確認到溶解剩下之 影殘渣。 〜 又，若於與上述相同之步驟中將顯影時間定為3〇秒， 則未曝光部之残渣消失，但於圖案的一部份見到缺陷。由 上可知，苯乙烯與乙烯基甲苯相比，顯影時間之容許幅度， 亦即顯影界限非常狹窄，且鹼顯影性差。 由上述之實施例以及比較例可知，本發明之聚合物重 量減少率小且耐熱分解性優異，同時溶劑溶解性、鹼顯影 性亦優異。 ' 本發明之聚合物本質的技術特徵在於：就形成其之單 體成分來說，使用於聚合物中會具有環結構之單體以及具 有S文基之單體之外，係使用乙烯基甲笨。 23 200914474 本發明之特徵之一係：N取代馬來醯亞胺單體及/或上 述通式（1)所表示之醚二聚物系單體會形成環結構，並藉由 此種結構而展現聚合物之耐熱性。由上述之該等化學結構 可明瞭：上述實施例中所使用之單體係上述單體群之一 例’只要是稱為N取代馬來醯亞胺單體以及/或醚二聚物 系單體之範疇的單體即可展現本發明效果。 又，就形成聚合物之單體成分來說，係藉由使用上述 3成分而可使結構中實質上不具有酯鍵結，因此，财熱性 便提高。本發明本質之特徵在於：在苯乙烯、乙烯基曱苯 等不具有酯鍵結之單體中，使用乙烯基甲苯，此可由上述 實施例、比較例證明。 成分之比例若在 可達到有利之效 此外，上述實施例中亦證明了上述3 本5兒明書中所記載之較佳範圍内則本發明 (產業利用性）Isy 潜 肊 ® ® ® ® ® ® ® ® ® ® 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 砩驴 s s s s s s s s s s s s s s s s φ φ φίτ1Γ¥« (%), ^\^®w« (, # ornSE^^蘧) inverted (, # otNsa赀磙蹑)拉傲(#οεΪΕ赍轮蘧)銎茏雠B is^i0 $ i $ si 200914474 Example 2 As shown in Table 1, the N-benzyl maleimide was substituted for dimethyl 2,2-[oxybis(methylenebis)]_2-acrylic acid vinegar. In addition, the coating film and the cured film were produced by the same operation as in Example 1, and the physical properties and the like were measured. The time during which the coating film was dissolved in PGMEA was 14 seconds. Further, the cured film was at 230 ° C for 30 minutes. The weight reduction rate was 〇6%. Example 3 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) and 50 parts of propylene glycol monomethyl ether (PGME) were added to a separable flask as a cooling tube with a reaction vessel. After nitrogen substitution, the temperature is raised to 9 〇. On the other hand, in the dropping tank 1, N-benzyl maleimide 15 parts, 37 2 parts of acrylic acid, and peroxy-2-ethylhexanoic acid third Ester 2·〇 part, pGMEA 56 parts, pGME 24 parts are mixed. Also, the vinyl is dropped in the groove 2 47 parts of toluene (mixture of m-vinyltoluene and p-vinyl fluorene to 60 to 4 )) and 47 parts of n-dodecylmercaptan were mixed, while maintaining the reaction temperature at 9 Torr. Drip into the reaction tank at a constant rate from the dropping tank and 2 at 4.0 hours. After the completion of the dropwise addition, after maintaining at 90 ° C for 30 minutes, 0.5 parts of peroxy-2-ethylhexanoic acid third butyl vinegar was added, and then 90 The reaction was continued for 30 minutes at ° C. Thereafter, the reaction temperature was raised to 11 5 ° C, and the reaction was continued for 1.5 hours. Once cooled to room temperature, glycidyl methacrylate 50 〇 、, 6 _ third butyl Base-2,4 - 曱 曱 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 The reaction was completed in the same manner as in Example 1, 21 200914474, and then cooled to room temperature to obtain a polymer solution. The obtained polymer solution had a weight average molecular weight of 13 Å and a solid content concentration of 36.1%. The acid value of the solid component was 8 〇 mg K 〇 H / g. The same preparation as in Example 1 was carried out. The coating film was formed until the time when the hydrazine was dissolved in pgmea was 16 seconds. The weight reduction rate when the cured film was held at 23 ° C for 30 minutes as measured by the TG-DTA method was 〇.6 〇 / 0. The Uv light of 50 mJ/cm2 was exposed to a uv exposure apparatus (TME_150RNS manufactured by Topcon Co., Ltd.) through a line width of 15/zm and a spacer mask (1) (10) & space mask. After drying for 3 minutes, the resultant was developed by a Suraker developing machine (ADE_3〇〇〇s manufactured by Actes Co., Ltd.) with a k〇h water/liquid mixture of 〇1 for 20 seconds. The figure shows the state of the glass substrate after alkali-developing the coating film after exposure. In Fig. 1, the lattice portion (rectangular pattern) located at the upper portion is an exposed portion exposed through the reticle, and the periphery thereof is an unexposed portion protected by the reticle. As shown in Fig. 1, a complete pattern was formed in the exposed portion due to curing of the coating film. When the unexposed portion was formed, the coating film was dissolved, and it was confirmed that the remaining residue was not dissolved. Further, even if the development time in the same step as described above was set to 30 seconds, there was no pattern defect. Comparative Example 1 The same operation as in Example ’ was carried out except that benzyl methyl methacrylate was used instead of ethylene toluene. The dissolution time of the coating film was 10 seconds, and at 23 Torr, the weight reduction rate at 30 minutes was 35%. Comparative Example 2 22 200914474 The same operation as in Example 1 was carried out except that styrene-substituted vinyl toluene was used as shown in Table 1. The dissolution time of the coating film was 24, which was slower than that of Example 1. Further, the weight reduction rate at 230 ° C for 30 minutes was 1.4%. 〇 Comparative Example 3 The same operation as in Example 3 was carried out except that styrene was used instead of vinyl benzene. The coating film was dissolved to PGMEA > 々 < dissolution time was 30 seconds, which was longer than that of Example 3. The weight reduction rate of the cured film at 230 C for 30 minutes was 11%. Alkali development was carried out under the same conditions as in Example 3. Fig. 2 is a view showing a state of a glass substrate obtained by alkali-developing a coating film after exposure, and in the same manner as in Fig. 1, an exposed portion and an unexposed portion are formed. As shown in Fig. 2, the exposure portion is formed with a pattern. In the unexposed portion, the coating film was not dissolved, and it was confirmed that the remaining film residue was dissolved. Further, if the development time is set to 3 sec seconds in the same procedure as described above, the residue of the unexposed portion disappears, but defects are observed in a part of the pattern. As is apparent from the above, the allowable range of development time, that is, the development limit of styrene and vinyl toluene is extremely narrow, and the alkali developability is poor. As is apparent from the above examples and comparative examples, the polymer of the present invention has a small weight reduction rate and is excellent in thermal decomposition resistance, and is excellent in solvent solubility and alkali developability. The technical essence of the polymer of the present invention is that, in terms of the monomer component forming the same, it is used for a monomer having a ring structure and a monomer having a S-group in the polymer, and a vinyl group is used. stupid. 23 200914474 One of the features of the present invention is that the N-substituted maleimide monomer and/or the ether dimer monomer represented by the above formula (1) form a ring structure, and by such a structure Shows the heat resistance of the polymer. From the above-mentioned chemical structures, it is clear that one of the above-mentioned monomer groups of the single system used in the above examples is as long as it is called an N-substituted maleimide monomer and/or an ether dimer monomer. The monomer of the category can exhibit the effects of the present invention. Further, in the case where the monomer component of the polymer is formed, the above-mentioned three components can be used to substantially eliminate the ester bond in the structure, so that the heat-treating property is improved. The essence of the present invention is that vinyltoluene is used in a monomer having no ester bond such as styrene or vinyl anthracene, which can be exemplified by the above examples. The ratio of the components can be advantageous, and the above embodiment also proves that the present invention (industrial use) is within the preferred range described in the above three books.
脂、各種塗佈材料。 ，液晶顯示器、印刷配線 劑高分子、熱硬化性樹Grease, various coating materials. , liquid crystal display, printed wiring agent polymer, thermosetting tree
張優先權。 該申請之内容係全部援 J作為基礎，主 曰於日本所申請之曰本 新頡聚合物」作為基礎，主 用於本申請案中作為參 【圓式簡單說明】 24 200914474 圖1係表示實施例3中鹼顯影後之基板狀態圖 圖2係表示比較例3中鹼顯影後之基板狀態圖。 【主要元件符號說明】 無 25Zhang priority. The content of this application is based on the full support of J, and is based on the 颉本新颉polymer applied for in Japan. It is mainly used in this application as a reference [round simple description] 24 200914474 Figure 1 shows the implementation Fig. 2 is a diagram showing the state of the substrate after alkali development in Comparative Example 3. Fig. 2 is a view showing the state of the substrate after alkali development in Comparative Example 3. [Main component symbol description] None 25
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| CN103848930A (en) * | 2013-12-30 | 2014-06-11 | 苏州瑞红电子化学品有限公司 | Synthesis of N-phenyl maleimide-containing photosensitive acrylic resin and application thereof in negative photoresist |
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| JP5615123B2 (en) * | 2010-10-12 | 2014-10-29 | 株式会社日本触媒 | Polymer and its use |
| JP6166526B2 (en) * | 2011-12-09 | 2017-07-19 | 株式会社日本触媒 | Curable resin composition and use thereof |
| JP2013167786A (en) * | 2012-02-16 | 2013-08-29 | Mitsubishi Chemicals Corp | Curable resin composition for organic insulating film, cured material, tft active matrix substrate, and liquid-crystal display |
| JP6095416B2 (en) * | 2012-10-08 | 2017-03-15 | 株式会社日本触媒 | Styrene polymer solution |
| TWI627504B (en) * | 2015-08-11 | 2018-06-21 | 奇美實業股份有限公司 | Photosensitive resin composition for color filters and uses thereof |
| CN111149058B (en) * | 2017-09-22 | 2024-03-08 | 东丽株式会社 | Transparent photosensitive resin composition and application thereof, photoetching spacer, liquid crystal display device and manufacturing method thereof |
| WO2019124144A1 (en) | 2017-12-18 | 2019-06-27 | 株式会社日本触媒 | Polymer, curable resin composition and use thereof |
| JP2023127081A (en) * | 2022-03-01 | 2023-09-13 | 株式会社日本触媒 | Polymer for carbon nanotube dispersion and carbon nanotube dispersion liquid |
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| JP3867177B2 (en) * | 1997-04-30 | 2007-01-10 | Ｊｓｒ株式会社 | Radiation sensitive composition for color filter |
| TWI250996B (en) * | 1999-09-01 | 2006-03-11 | Jsr Corp | Curable composition and color filter protective film |
| JP2003082073A (en) * | 2001-09-11 | 2003-03-19 | Nippon Petrochemicals Co Ltd | Cyclic olefin monomer composition, production method thereof, cyclic olefin polymer composition and cyclic olefin polymer hydrogenated composition |
| JP2004224894A (en) * | 2003-01-22 | 2004-08-12 | Nippon Shokubai Co Ltd | Maleimide copolymer |
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| JP2005239999A (en) * | 2004-01-27 | 2005-09-08 | Nippon Shokubai Co Ltd | Resin composition for forming visible light, near infrared ray or neon light absorbing layer |
| JP2006089528A (en) * | 2004-09-21 | 2006-04-06 | Nippon Shokubai Co Ltd | Led sealant, light emitting diode including the same and curable composition |
| JP4852935B2 (en) * | 2005-08-30 | 2012-01-11 | 三菱化学株式会社 | Color material dispersion, colored resin composition, color filter, and liquid crystal display device |
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| JP2008056867A (en) * | 2006-09-04 | 2008-03-13 | The Inctec Inc | Pigment dispersion and colored photosensitive composition |
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