KR101279614B1 - Alkali soluble resin polymer with fluorene group, method of manufacturing the polymer and negative photosensitive resin composition including the polymer - Google Patents
Alkali soluble resin polymer with fluorene group, method of manufacturing the polymer and negative photosensitive resin composition including the polymer Download PDFInfo
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- KR101279614B1 KR101279614B1 KR1020080112068A KR20080112068A KR101279614B1 KR 101279614 B1 KR101279614 B1 KR 101279614B1 KR 1020080112068 A KR1020080112068 A KR 1020080112068A KR 20080112068 A KR20080112068 A KR 20080112068A KR 101279614 B1 KR101279614 B1 KR 101279614B1
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- oxy carbonyl
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- 239000011347 resin Substances 0.000 title claims abstract description 67
- 229920005989 resin Polymers 0.000 title claims abstract description 67
- 229920000642 polymer Polymers 0.000 title claims abstract description 41
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- 239000003513 alkali Substances 0.000 title claims description 7
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 3
- -1 methyl oxy carbonyl group Chemical group 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011230 binding agent Substances 0.000 claims abstract description 39
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 21
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 15
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 claims abstract description 11
- 125000005929 isobutyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC(*)=O 0.000 claims abstract description 11
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims abstract description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 9
- 239000002253 acid Substances 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 9
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- ALIATVYMFGMEJC-UHFFFAOYSA-N phenyl-[2,4,6-tris(methylamino)phenyl]methanone Chemical compound CNC1=CC(NC)=CC(NC)=C1C(=O)C1=CC=CC=C1 ALIATVYMFGMEJC-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 150000002431 hydrogen Chemical class 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 229920005822 acrylic binder Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 238000012719 thermal polymerization Methods 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 5
- 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 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 229940024874 benzophenone Drugs 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ROVRRJSRRSGUOL-UHFFFAOYSA-N victoria blue bo Chemical compound [Cl-].C12=CC=CC=C2C(NCC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 ROVRRJSRRSGUOL-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C08F220/10—Esters
-
- 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
-
- 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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
Abstract
본 발명은 플루오렌 그룹을 포함하는 알칼리 가용성 수지 중합체와, 이의 제조방법 및 이를 포함하는 네가티브형 감광성 수지 조성물에 관한 것으로, 하기 화학식 1의 화합물과 아크릴산 또는 메타크릴산의 반응에 의한 플루오렌계 화합물을, 하기 화학식 4의 화합물과 하기 화학식 5의 화합물을 단위체로 하는 알칼리 가용성 바인더 수지에 반응시킨 플루오렌을 포함하는 알칼리 가용성 바인더 수지 중합체에 관한 것이다.The present invention relates to an alkali-soluble resin polymer containing a fluorene group, a method for preparing the same, and a negative photosensitive resin composition including the same, and a fluorene-based compound obtained by reaction of a compound of Formula 1 with acrylic acid or methacrylic acid The present invention relates to an alkali-soluble binder resin polymer containing fluorene reacted with an alkali-soluble binder resin containing a compound of formula (4) and a compound of formula (5) as a unit.
[화학식 1][Formula 1]
(상기 식에서, X는 탄소 1 ~ 3 의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이다.)(Wherein, X is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide of 1 to 3 carbons.)
[화학식 4][Formula 4]
(상기 식에서, R2는 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이고, A는 페닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기 또는 이소보닐 옥시 카보닐기이다.)Wherein R 2 is hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, and A is a phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy carbon And a cyclohexyl oxy carbonyl group or isobornyl oxy carbonyl group.)
[화학식 5][Chemical Formula 5]
(상기 식에서, R3은 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이다.)(Wherein, R 3 is hydrogen, an alkyl group of 1 to 3 carbon atoms or an alkoxy group.)
본 발명에 따른 중합체에 의하면, 감도, 내화학성 및 상용성이 우수한 감광성 수지 조성물을 제공할 수 있다.According to the polymer which concerns on this invention, the photosensitive resin composition excellent in the sensitivity, chemical resistance, and compatibility can be provided.
플루오렌, 알칼리 가용성 수지, 감광성 수지 조성물, 감도, 내화학성, 상용성 Fluorene, alkali-soluble resin, photosensitive resin composition, sensitivity, chemical resistance, compatibility
Description
본 발명은 플루오렌 그룹을 포함하는 알칼리 가용성 수지 중합체와, 이의 제조방법 및 이를 포함하는 네가티브형 감광성 수지 조성물에 관한 것으로, 보다 상세하게는 아크릴계 바인더 수지에 플루오렌 그룹을 포함하는 화합물을 반응시킴으로써 적절한 분자량 및 산가를 갖는 플로렌계 수지 중합체에 관한 것이다. The present invention relates to an alkali-soluble resin polymer containing a fluorene group, a method for preparing the same, and a negative photosensitive resin composition comprising the same, and more particularly, by reacting a compound containing a fluorene group with an acrylic binder resin. The present invention relates to a florene resin polymer having a molecular weight and an acid value.
일반적으로 감광성 수지 조성물은 액정표시장치를 구성하는 컬러 필터, 블랙 매트릭스, 오버코트 및 컬럼 스페이서 등과 같은 분야에서 다양하게 사용될 수 있으며, 그 중에서 특히 플루오렌 그룹을 포함하는 카도계 바인더수지는 고감도이면서 내열성, 내화학성 등이 우수하여 블랙 매트릭스를 형성하는 감광성 수지 조성물에 많이 사용되고 있다. In general, the photosensitive resin composition may be used in various fields such as color filters, black matrices, overcoats and column spacers constituting the liquid crystal display device. Among them, a cardo-based binder resin including fluorene group is particularly sensitive and heat resistant. It is used for the photosensitive resin composition which is excellent in chemical resistance etc. and forms a black matrix.
하지만 기존에 알려져 있는 플루오렌계 수지의 합성방법은 플루오렌기를 포함하는 디에폭시 화합물에 아크릴산을 반응시켜 디올 화합물을 얻은 후, 이를 산이무수물과 반응시키는 것인데, 이러한 합성방법은 최종적으로 알콜기와 무수물기가 반응하면서 액시드 그룹을 형성시키기 때문에 중합반응이 진행될수록 분자량과 함께 산가도 크게 증가한다는 단점이 있다.However, the known synthesis method of fluorene-based resin is to react the diepoxy compound containing a fluorene group with acrylic acid to obtain a diol compound, and then react with an acid dianhydride. Since acid groups are formed during the reaction, there is a disadvantage in that the acid value increases with the molecular weight as the polymerization reaction proceeds.
따라서 이와 같은 종래의 플루오렌계 수지 중합체는 분자량 대비 높은 산가를 갖고 있기 때문에 블랙 매트릭스용 감광성 수지 조성물에 적용했을 때, 현상시 패턴 깎임 현상 및 패턴 끝단의 탈락이 심해져 전체적인 패턴의 직진성을 저하시키며, 감광성 수지 조성물 내의 다른 화합물과의 상용성도 좋지 못한 문제점을 발생시킨다.Therefore, since the conventional fluorene-based resin polymer has a high acid value compared to the molecular weight, when applied to the photosensitive resin composition for black matrix, pattern shaping phenomenon and dropping of the end of the pattern is severe during development, thereby reducing the straightness of the overall pattern, The compatibility with other compounds in the photosensitive resin composition also causes problems.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 산기를 포함하는 아크릴계 바인더 수지에 플루오렌 그룹을 포함하는 화합물을 반응시킴으로써, 적절한 분자량 및 산가를 갖는 플로렌계 수지 중합체를 제공하는 것을 그 목적으로 한다.The present invention has been made to solve the above problems, and by reacting a compound containing a fluorene group to an acrylic binder resin containing an acid group, to provide a florene resin polymer having an appropriate molecular weight and acid value. do.
본 발명은 상기의 목적을 달성하기 위한 것으로, 하기 화학식 1의 화합물과 아크릴산 또는 메타크릴산의 반응에 의한 플루오렌계 화합물을, 하기 화학식 4의 화합물과 하기 화학식 5의 화합물을 단위체로 하는 알칼리 가용성 바인더 수지에 반응시킨 플루오렌을 포함하는 알칼리 가용성 바인더 수지 중합체를 제공한다.The present invention is to achieve the above object, an alkali-soluble fluorene-based compound by the reaction of the compound of formula (1) and acrylic acid or methacrylic acid, the compound of formula (4) and the compound of formula (5) as a unit An alkali-soluble binder resin polymer comprising fluorene reacted with a binder resin is provided.
[화학식 1][Formula 1]
(상기 식에서, X는 탄소 1 ~ 3 의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이다.)(Wherein, X is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide of 1 to 3 carbons.)
[화학식 4][Formula 4]
(상기 식에서, R2는 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이고, A는 페닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기 또는 이소보닐 옥시 카보닐기이다.)Wherein R 2 is hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, and A is a phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy carbon And a cyclohexyl oxy carbonyl group or isobornyl oxy carbonyl group.)
[화학식 5][Chemical Formula 5]
(상기 식에서, R3은 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이다.)(Wherein, R 3 is hydrogen, an alkyl group of 1 to 3 carbon atoms or an alkoxy group.)
또한, 상기 바인더 수지 중합체는 하기 화학식 6으로 표시되는 중합체인 것을 특징으로 한다.In addition, the binder resin polymer is characterized in that the polymer represented by the formula (6).
[화학식 6] [Chemical Formula 6]
(상기 식에서, X는 탄소 1 ~ 3 의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이고, R1 및 R3은 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이고, R2는 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이고, A는 페닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기 또는 이소보닐 옥시 카보닐기이고, a, b, c 는 몰 혼합비로서, 각각 10 ~ 40이다.)Wherein X is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide of 1 to 3 carbon atoms, R 1 and R 3 are hydrogen, an alkyl group or alkoxy group of 1 to 3 carbon atoms, and R 2 is hydrogen , An alkyl group having 1 to 3 carbon atoms or an alkoxy group, A is a phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy carbonyl group, cyclohexyl oxy carbonyl group or Isobonyl oxycarbonyl group, a, b, c are molar mixing ratios, each of 10 to 40.)
또한, 상기 바인더 수지 중합체의 산가는 30 ~ 150KOHmg/g이고, 폴리스티렌 환산 중량평균분자량이 3000 ~ 30000g/mol인 것을 특징으로 한다.In addition, the acid value of the binder resin polymer is 30 ~ 150KOHmg / g, the weight average molecular weight in terms of polystyrene is characterized in that 3000 ~ 30000g / mol.
또한, 본 발명은 하기 화학식 1의 화합물과 아크릴산 또는 메타크릴산을 반응시켜 하기 화학식 2의 화합물을 수득하는 단계; 하기 화학식 4의 화합물과 하기 화학식 5의 화합물을 중합하여 알칼리 가용성 바인더 수지를 제조하는 단계; 및 상기 화학식 2의 화합물 및 상기 알칼리 가용성 바인더 수지를 반응시켜 플루오렌을 포함하는 알칼리 가용성 바인더 수지 중합체를 제조하는 방법을 제공한다.In addition, the present invention comprises the steps of reacting a compound of the formula (1) and acrylic acid or methacrylic acid to obtain a compound of the formula (2); Preparing an alkali-soluble binder resin by polymerizing a compound of Formula 4 with a compound of Formula 5; And it provides a method for producing an alkali-soluble binder resin polymer containing fluorene by reacting the compound of Formula 2 and the alkali-soluble binder resin.
[화학식 1][Formula 1]
(상기 식에서, X는 탄소 1 ~ 3 의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이다.)(Wherein, X is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide of 1 to 3 carbons.)
[화학식 2][Formula 2]
(상기 식에서, X는 탄소 1 ~ 3 의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이고, R1은 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이다.)(Wherein, X is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide of 1 to 3 carbon, R 1 is hydrogen, an alkyl group or alkoxy group of 1 to 3 carbon.)
[화학식 4][Formula 4]
(상기 식에서, R2는 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이고, A는 페닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기 또는 이소보닐 옥시 카보닐기이다.)Wherein R 2 is hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, and A is a phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy carbon And a cyclohexyl oxy carbonyl group or isobornyl oxy carbonyl group.)
[화학식 5][Chemical Formula 5]
(상기 식에서, R3은 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이다.)(Wherein, R 3 is hydrogen, an alkyl group of 1 to 3 carbon atoms or an alkoxy group.)
또한, 본 발명은 상기의 알칼리 가용성 바인더 수지 중합체, 에틸렌성 불포화 결합을 갖는 중합성 화합물, 광개시제, 및 용매를 포함하는 감광성 수지 조성물을 제공한다.Moreover, this invention provides the photosensitive resin composition containing the said alkali-soluble binder resin polymer, the polymeric compound which has an ethylenically unsaturated bond, a photoinitiator, and a solvent.
또한, 상기 구성성분의 함량은 알칼리 가용성 바인더 수지 중합체 1 ~ 20중량부, 에틸렌성 불포화 결합을 갖는 중합성 화합물 0.5 ~ 10중량부, 광개시제 0.1 ~ 5중량부, 및 용매 10 ~ 95중량부인 것을 특징으로 한다.In addition, the content of the component is 1 to 20 parts by weight of an alkali-soluble binder resin polymer, 0.5 to 10 parts by weight of a polymerizable compound having an ethylenically unsaturated bond, 0.1 to 5 parts by weight of a photoinitiator, and 10 to 95 parts by weight of a solvent. It is done.
또한, 상기 수지 조성물은 네가티브형 칼라필터용 감광재 또는 블랙매트릭스용 감광재로 사용되며, 이 경우 착색제 0.5 ~ 20중량부를 더 포함하는 것을 특징으로 한다.In addition, the resin composition is used as a photosensitive material for a negative color filter or a photosensitive material for a black matrix, in this case characterized in that it further comprises 0.5 to 20 parts by weight of a colorant.
또한, 상기 에틸렌성 불포화 결합을 갖는 중합성 화합물은 펜타에리스리톨 트리(메타)아크릴레이트, 펜타에리스리톨 테트라(메타)아크릴레이트, 에틸렌 글리콜 디(메타)아크릴레이트, 또는 폴리에틸렌 글리콜 디(메타)아크릴레이트인 것을 특징으로 한다.The polymerizable compound having an ethylenically unsaturated bond is pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, or polyethylene glycol di (meth) acrylate. It is characterized by.
또한, 상기 광개시제는 2,4-트리클로로메틸-(4'-메톡시페닐)-6-트리아진, 2,4-트리클로로메틸-(4'-메톡시스티릴)-6-트리아진, 2,4-트리클로로메틸-(피플로닐)-6-트리아진, 1-히드록시시클로헥실 페닐 케톤, 4-(2-히드록시에톡시)-페닐 (2-히드록시)프로필 케톤, 벤조페논, 또는 2,4,6-트리메틸아미노벤조페논인 것을 특징으로 한다.Further, the photoinitiator is 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine, 2,4-trichloromethyl- (piflonyl) -6-triazine, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy) propyl ketone, benzo Phenone or 2,4,6-trimethylaminobenzophenone.
또한, 상기 용매는 메틸 에틸 케톤, 프로필렌 글리콜 디에틸 에테르, 프로필렌 글리콜 메틸 에테르 아세테이트, 3-메톡시부틸 아세테이트, 또는 디프로필렌 글리콜 모노메틸 에테르인 것을 특징으로 한다.In addition, the solvent is characterized in that methyl ethyl ketone, propylene glycol diethyl ether, propylene glycol methyl ether acetate, 3-methoxybutyl acetate, or dipropylene glycol monomethyl ether.
본 발명에 따른 플루오렌 그룹을 포함하는 알칼리 가용성 수지 중합체에 의하면, 감도 및 내화학성이 우수하며, 감광성 수지 조성물 내의 다른 화합물과의 상용성이 우수한 알칼리 가용성 수지 중합체를 포함하는 감광성 수지 조성물을 제공 할 수 있다. According to the alkali-soluble resin polymer containing a fluorene group according to the present invention, it is possible to provide a photosensitive resin composition comprising an alkali-soluble resin polymer excellent in sensitivity and chemical resistance, and excellent in compatibility with other compounds in the photosensitive resin composition. Can be.
본 발명은 하기 화학식 1의 화합물과 아크릴산 또는 메타크릴산의 반응에 의한 플루오렌계 화합물을, 하기 화학식 4의 화합물과 하기 화학식 5의 화합물을 단위체로 하는 알칼리 가용성 바인더 수지에 반응시킨 플루오렌을 포함하는 알칼리 가용성 바인더 수지 중합체에 관한 것이다.The present invention includes a fluorene obtained by reacting a fluorene-based compound by a reaction of a compound of Formula 1 with acrylic acid or methacrylic acid to an alkali-soluble binder resin containing a compound of Formula 4 and a compound of Formula 5 as a unit It relates to an alkali-soluble binder resin polymer.
[화학식 1][Formula 1]
(상기 식에서, X는 탄소 1 ~ 3 의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이다.)(Wherein, X is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide of 1 to 3 carbons.)
[화학식 4][Formula 4]
(상기 식에서, R2는 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이고, A는 페 닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기 또는 이소보닐 옥시 카보닐기이다.)Wherein R 2 is hydrogen, an alkyl group of 1 to 3 carbon atoms or an alkoxy group, A is a phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy Carbonyl group, cyclohexyl oxy carbonyl group or isobonyl oxy carbonyl group.)
[화학식 5][Chemical Formula 5]
(상기 식에서, R3은 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이다.)(Wherein, R 3 is hydrogen, an alkyl group of 1 to 3 carbon atoms or an alkoxy group.)
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 하기 화학식 1로 표기되는 플루오렌 골격을 갖는 디에폭시 화합물과 아크릴산 또는 메타크릴산을 적절한 비율로 반응시켜 하기 화학식 2로 표기되는 화합물을 합성한 후, 이를 적절한 분자량 및 산가를 갖는 아크릴계 바인더 수지와 반응시킴으로써 하기 화학식 6 과 같은 바인더 수지를 제공한다. 상기 아크릴계 바인더 수지는 하기 화학식 4 및 화학식 5의 단량체가 중합된 것이다.The present invention synthesizes a compound represented by the following Chemical Formula 2 by reacting a diepoxy compound having a fluorene skeleton represented by the following Chemical Formula 1 with acrylic acid or methacrylic acid at an appropriate ratio, and then, an acrylic binder having an appropriate molecular weight and acid value. By reacting with a resin to provide a binder resin, such as the formula (6). The acrylic binder resin is polymerized monomers of the following formula (4) and (5).
[화학식 1][Formula 1]
(상기 식에서, X는 탄소 1 ~ 3 의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이다.)(Wherein, X is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide of 1 to 3 carbons.)
[화학식 2][Formula 2]
(상기 식에서, X는 탄소 1 ~ 3 의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이고, R1은 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이다.)(Wherein, X is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide of 1 to 3 carbon, R 1 is hydrogen, an alkyl group or alkoxy group of 1 to 3 carbon.)
[화학식 4][Formula 4]
(상기 식에서, R2는 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이고, A는 페닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기 또는 이소보닐 옥시 카보닐기이다.)Wherein R 2 is hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, and A is a phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy carbon And a cyclohexyl oxy carbonyl group or isobornyl oxy carbonyl group.)
[화학식 5][Chemical Formula 5]
(상기 식에서, R3은 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이다.)(Wherein, R 3 is hydrogen, an alkyl group of 1 to 3 carbon atoms or an alkoxy group.)
[화학식 6] [Formula 6]
(상기 식에서, X는 탄소 1 ~ 3 의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이고, R1 및 R3은 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이고, R2는 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이고, A는 페닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기 또는 이소보닐 옥시 카보닐기이고, a, b, c 는 몰 혼합비로서, 각각 10 ~ 40이다.)Wherein X is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide of 1 to 3 carbon atoms, R 1 and R 3 are hydrogen, an alkyl group or alkoxy group of 1 to 3 carbon atoms, and R 2 is hydrogen , An alkyl group having 1 to 3 carbon atoms or an alkoxy group, A is a phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy carbonyl group, cyclohexyl oxy carbonyl group or Isobonyl oxycarbonyl group, a, b, c are molar mixing ratios, each of 10 to 40.)
본 발명의 일실시예로 상기 화학식 2 에서 X가 메틸렌기이고, R1이 수소인 경우 하기 화학식 3 과 같이 표시될 수 있다. In one embodiment of the present invention, when X is a methylene group and R 1 is hydrogen in Formula 2, it may be represented as in Formula 3.
[화학식 3](3)
또한, 보다 구체적으로 하기 화학식 7 과 같이 표기되는 바인더를 포함한다. In addition, more specifically, a binder represented by the following Chemical Formula 7 is included.
[화학식 7] [Formula 7]
(상기 식에서, a, b, c 는 몰 혼합비로서, 각각 10 ~ 40이다.)(Wherein a, b, and c are molar mixing ratios, each of 10 to 40).
본 발명에 따른 플루오렌 화합물을 포함하는 아크릴계 알칼리 가용성 수지는 산가가 30 ~ 150 KOH mg/g 인 것이 바람직하며, 중량 평균 분자량이 3,000 ~ 30,000 g/mol 의 범위를 갖는 것이 바람직하다. The acrylic alkali-soluble resin containing the fluorene compound according to the present invention preferably has an acid value of 30 to 150 KOH mg / g, and preferably has a weight average molecular weight of 3,000 to 30,000 g / mol.
또한, 본 발명은 하기와 같은 플루오렌을 포함하는 알칼리 가용성 바인더 수 지 중합체의 제조방법을 제공한다.The present invention also provides a method for producing an alkali-soluble binder resin polymer containing fluorene as follows.
하기 화학식 1의 화합물과 아크릴산 또는 메타크릴산을 반응시켜 하기 화학식 2의 화합물을 수득하는 단계; Reacting a compound of Formula 1 with acrylic acid or methacrylic acid to obtain a compound of Formula 2;
하기 화학식 4의 화합물과 하기 화학식 5의 화합물을 중합하여 알칼리 가용성 바인더 수지를 제조하는 단계; 및Preparing an alkali-soluble binder resin by polymerizing a compound of Formula 4 with a compound of Formula 5; And
상기 화학식 2의 화합물 및 상기 알칼리 가용성 바인더 수지를 반응시켜 플루오렌을 포함하는 알칼리 가용성 바인더 수지 중합체를 제조하는 방법.A method of preparing an alkali-soluble binder resin polymer comprising fluorene by reacting the compound of Formula 2 and the alkali-soluble binder resin.
[화학식 1][Formula 1]
(상기 식에서, X는 탄소 1 ~ 3 의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이다.)(Wherein, X is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide of 1 to 3 carbons.)
[화학식 2][Formula 2]
(상기 식에서, X는 탄소 1 ~ 3 의 알킬렌, 에틸렌 옥사이드 및 프로필렌 옥사이드로 이루어진 군에서 선택된 하나이고, R1은 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이다.)(Wherein, X is one selected from the group consisting of alkylene, ethylene oxide and propylene oxide of 1 to 3 carbon, R 1 is hydrogen, an alkyl group or alkoxy group of 1 to 3 carbon.)
[화학식 4][Formula 4]
(상기 식에서, R2는 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이고, A는 페닐기, 벤질 옥시 카보닐기, 메틸 옥시 카보닐기, 에틸 옥시 카보닐기, 이소부틸 옥시 카보닐기, t-부틸 옥시 카보닐기, 사이클로 헥실 옥시 카보닐기 또는 이소보닐 옥시 카보닐기이다.)Wherein R 2 is hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, and A is a phenyl group, benzyl oxy carbonyl group, methyl oxy carbonyl group, ethyl oxy carbonyl group, isobutyl oxy carbonyl group, t-butyl oxy carbon And a cyclohexyl oxy carbonyl group or isobornyl oxy carbonyl group.)
[화학식 5][Chemical Formula 5]
(상기 식에서, R3은 수소, 탄소 1 ~ 3 의 알킬기 또는 알콕시기이다.)(Wherein, R 3 is hydrogen, an alkyl group of 1 to 3 carbon atoms or an alkoxy group.)
종래의 플루오렌계 수지 중합체는 플루오렌 그룹을 포함하는 디올 화합물과 산이무수물이 반응하여 얻어지는 시스템이기 때문에 반응이 진행되면서 중합체의 분자량과 함께 산가도 함께 높아진다는 단점이 있다. 따라서, 본 발명은 상기 문제점을 개선하기 위해, 적절한 분자량 및 산가를 갖는 아크릴계 바인더 수지를 먼저 합성한 후에, 다음 반응에서 플루오렌계 화합물을 반응시키는 합성 방법을 사용하여, 플루오렌 그룹이 갖는 고감도, 내열성, 내화학성 등의 장점은 유지하면서 적당한 분자량 및 산가를 갖는 바인더 수지를 합성할 수 있도록 한 것이다.The conventional fluorene-based resin polymer is a system obtained by reacting a diol compound containing a fluorene group with an acid dianhydride, so that the acid value is increased together with the molecular weight of the polymer as the reaction proceeds. Therefore, in order to improve the above problems, the present invention uses a synthetic method of first synthesizing an acrylic binder resin having an appropriate molecular weight and an acid value, and then reacting a fluorene-based compound in the next reaction. The advantages of heat resistance, chemical resistance, and the like are to be synthesized while maintaining a binder resin having a suitable molecular weight and acid value.
또한, 본 발명은,Further, according to the present invention,
a) 상기 플루오렌을 포함하는 알칼리 가용성 바인더 수지 중합체 1 내지 20 중량부;a) 1 to 20 parts by weight of an alkali-soluble binder resin polymer containing fluorene;
b) 에틸렌성 불포화 결합을 갖는 중합성 화합물 0.5 내지 10 중량부;b) 0.5 to 10 parts by weight of a polymerizable compound having an ethylenically unsaturated bond;
c) 광개시제 0.1 내지 5중량부; 및c) 0.1 to 5 parts by weight of photoinitiator; And
d) 용매 10 내지 95 중량부d) 10 to 95 parts by weight of solvent
로 함유되어 있는 감광성 수지 조성물을 제공한다. It provides the photosensitive resin composition contained in.
또한, 네가티브형 칼라필터용 감광재와 블랙 매트릭스용 감광재의 경우는 그 외의 첨가제로서 착색제 0.5 내지 20 중량부를 포함한다. In addition, the photosensitive material for negative color filters and the photosensitive material for black matrices contain 0.5-20 weight part of coloring agents as other additives.
상기 b)의 에틸렌성 불포화 결합을 갖는 중합성 화합물로는 펜타에리스리톨 트리(메타)아크릴레이트, 펜타에리스리톨 테트라(메타)아크릴레이트, 에틸렌 글리콜 디(메타)아크릴레이트, 폴리에틸렌 글리콜 디(메타)아크릴레이트 등의 화합물 중에서 선택될 수 있다. Examples of the polymerizable compound having an ethylenically unsaturated bond in b) include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. It may be selected from compounds such as.
상기 c)의 광개시제로는 2,4-트리클로로메틸-(4'-메톡시페닐)-6-트리아진, 2,4-트리클로로메틸-(4'-메톡시스티릴)-6-트리아진, 2,4-트리클로로메틸-(피플로닐)-6-트리아진 등의 트리아진 화합물; 1-히드록시시클로헥실 페닐 케톤, 4-(2-히드록시에톡시)-페닐 (2-히드록시)프로필 케톤 등의 아세토페논계 화합물; 벤조페논, 2,4,6-트리메틸아미노벤조페논 등의 벤조페논계 화합물 등에서 선택되는 1종 이상의 화합물이 사용될 수 있다. The photoinitiator of c) is 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-tri Triazine compounds such as azine and 2,4-trichloromethyl- (pipelonyl) -6-triazine; Acetophenone compounds such as 1-hydroxycyclohexyl phenyl ketone and 4- (2-hydroxyethoxy) -phenyl (2-hydroxy) propyl ketone; One or more compounds selected from benzophenone compounds such as benzophenone and 2,4,6-trimethylaminobenzophenone can be used.
상기 d)의 용매로는 메틸 에틸 케톤, 프로필렌 글리콜 디에틸 에테르, 프로필렌 글리콜 메틸 에테르 아세테이트, 3-메톡시부틸 아세테이트, 디프로필렌 글리 콜 모노메틸 에테르 등이 사용될 수 있다. As the solvent of d), methyl ethyl ketone, propylene glycol diethyl ether, propylene glycol methyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether, and the like may be used.
그 외에 감광성 수지 조성물에 포함될 수 있는 착색제로 흑색안료, 레드안료, 옐로우안료, 블루안료, 바이올렛안료 등에서 1 내지 2종 이상을 사용할 수 있다. 흑색안료의 예로는 카본블랙, 티탄블랙 등이 있고, 컬러안료로는 프탈로시아닌 그린, 프탈로시아닌 블루, 페릴렌 블랙, 리놀 옐로우, 빅토리아 퓨어 블루 등이 있다. In addition, as the colorant which may be included in the photosensitive resin composition, one or two or more kinds of black pigments, red pigments, yellow pigments, blue pigments, violet pigments, and the like may be used. Examples of black pigments include carbon black and titanium black, and color pigments include phthalocyanine green, phthalocyanine blue, perylene black, linol yellow, and Victoria pure blue.
이하, 본 발명의 실시예를 통해 본 발명에 대해 상세히 설명한다. Hereinafter, the present invention will be described in detail through embodiments of the present invention.
[실시예][Example]
[합성예 1]Synthesis Example 1
(플루오렌계 화합물의 합성)Synthesis of Fluorene Compound
9,9-비스페놀플루오렌디글리시딜에테르 104g과 아크릴산 16g, 테트라부틸 암모늄 브로마이드 0.7g, 열중합 금지제 MEHQ 0.08g 을 120g의 3-메톡시부틸 아세테이트와 프로필렌 글리콜 모노메틸 에테르 아세테이트 5 : 5 혼합 용매와 함께 교반하고, 반응기 내부에 산소를 흘려주며 반응기를 110℃로 가열하였다. 10시간 후 반응을 종료하여 플루오렌계 화합물을 얻었다. (고형분 47.93%, 분자량 534 g/mol)104 g of 9,9-bisphenolfluorene diglycidyl ether, 16 g of acrylic acid, 0.7 g of tetrabutyl ammonium bromide, 0.08 g of a thermal polymerization inhibitor MEHQ, and 120 g of 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate 5: 5 The mixture was stirred with the mixed solvent, and the reactor was heated to 110 ° C. while flowing oxygen inside the reactor. After 10 hours, the reaction was terminated to obtain a fluorene compound. (47.93% solids, molecular weight 534 g / mol)
[합성예 2][Synthesis Example 2]
(알칼리 가용성 수지의 중합)(Polymerization of Alkali Soluble Resin)
벤질 메타아크릴레이트 70g, 메타아크릴산 20g, 3-머켑토프로핀산 2g 을 300g의 3-메톡시부틸 아세테이트와 프로필렌 글리콜 모노메틸 에테르 아세테이트 5 : 5 혼합 용매에 혼합하고 질소 분위기 하에서 반응기의 온도를 60℃로 높였다. 혼합물의 온도가 60℃가 되었을 때 열중합 개시제인 AIBN 3.2g을 넣고 12시간 동안 교반하였다. 12시간 후, 중합 수율 98.5%, 분자량 6,000 g/mol, 고형분 25% 의 아크릴계 바인더 수지를 얻었다. 70 g of benzyl methacrylate, 20 g of methacrylic acid, and 2 g of 3-mercetopropionic acid were mixed with 300 g of 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate 5: 5 mixed solvent, and the reactor temperature was maintained at 60 ° C. under a nitrogen atmosphere. Raised to. When the temperature of the mixture reached 60 ℃ was added 3.2g of AIBN, a thermal polymerization initiator, and stirred for 12 hours. After 12 hours, an acrylic binder resin having a polymerization yield of 98.5%, a molecular weight of 6,000 g / mol, and a solid content of 25% was obtained.
이 고분자 용액의 온도를 다시 80℃로 높인 후, 합성예 1에서 합성한 플루오렌계 화합물 35g을 넣고 110℃에서 12 시간 동안 교반하여 분자량 7,000 g/mol, 산가 98, 고형분 27% 의 플루오렌계 알칼리 가용성 바인더 수지를 얻었다. After raising the temperature of the polymer solution again to 80 ° C., 35 g of the fluorene compound synthesized in Synthesis Example 1 was added thereto, and stirred at 110 ° C. for 12 hours to obtain a molecular weight of 7,000 g / mol, an acid value of 98 and a solid content of 27%. Alkali-soluble binder resin was obtained.
[합성예 3][Synthesis Example 3]
(알칼리 가용성 수지의 중합)(Polymerization of Alkali Soluble Resin)
스티렌 50g, 메타아크릴산 20g, 3-머켑토프로핀산 2g 을 300g의 3-메톡시부틸 아세테이트와 프로필렌 글리콜 모노메틸 에테르 아세테이트 5 : 5 혼합 용매에 혼합하고 질소 분위기 하에서 반응기의 온도를 60℃로 높였다. 혼합물의 온도가 60℃가 되었을 때 열중합 개시제인 AIBN 2.6g을 넣고 12시간 동안 교반하였다. 12시간 후, 중합 수율 95.5%, 분자량 6,000 g/mol, 고형분 25% 의 아크릴계 바인더 수지를 얻었다. 50 g of styrene, 20 g of methacrylic acid and 2 g of 3-mercetopropionic acid were mixed with 300 g of 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate 5: 5 mixed solvent, and the temperature of the reactor was raised to 60 ° C. under a nitrogen atmosphere. When the temperature of the mixture reached 60 ° C., 2.6 g of AIBN, a thermal polymerization initiator, was added thereto, and the mixture was stirred for 12 hours. After 12 hours, an acrylic binder resin having a polymerization yield of 95.5%, a molecular weight of 6,000 g / mol and a solid content of 25% was obtained.
이 고분자 용액의 온도를 다시 80℃로 높인 후, 합성예 1에서 합성한 플루오 렌계 화합물 35g을 넣고 110℃에서 12 시간 동안 교반하여 분자량 7,000g/mol, 산가 95, 고형분 26.5% 의 플루오렌계 알칼리 가용성 바인더 수지를 얻었다. After raising the temperature of the polymer solution to 80 ° C. again, 35 g of the fluorene compound synthesized in Synthesis Example 1 was added thereto, and stirred at 110 ° C. for 12 hours to obtain a fluorene alkali having a molecular weight of 7,000 g / mol, an acid value of 95, and a solid content of 26.5%. Soluble binder resin was obtained.
[비교 합성예 1][Comparative Synthesis Example 1]
(알칼리 가용성 수지의 중합)(Polymerization of Alkali Soluble Resin)
벤질 메타아크릴레이트 70g, 메타아크릴산 20g, 3-머켑토프로핀산 2g 을 300g의 3-메톡시부틸 아세테이트와 프로필렌 글리콜 모노메틸 에테르 아세테이트 5 : 5 혼합 용매에 혼합하고 질소 분위기 하에서 반응기의 온도를 60℃로 높였다. 혼합물의 온도가 60℃가 되었을 때 열중합 개시제인 AIBN 3.2g을 넣고 12시간 동안 교반하였다. 12시간 후, 중합 수율 98.5%, 분자량 6,000 g/mol, 고형분 25% 의 아크릴계 바인더 수지를 얻었다. 70 g of benzyl methacrylate, 20 g of methacrylic acid, and 2 g of 3-mercetopropionic acid were mixed with 300 g of 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate 5: 5 mixed solvent, and the reactor temperature was maintained at 60 ° C. under a nitrogen atmosphere. Raised to. When the temperature of the mixture reached 60 ℃ was added 3.2g of AIBN, a thermal polymerization initiator, and stirred for 12 hours. After 12 hours, an acrylic binder resin having a polymerization yield of 98.5%, a molecular weight of 6,000 g / mol, and a solid content of 25% was obtained.
이 고분자 용액의 온도를 다시 80℃로 높이고, 테트라부틸암모늄 브로마이드 1g 과 열중합 금지제인 MEHQ 0.1g을 넣고 30분간 교반한 후, 글리시딜 메타아크릴레이트 12g 을 넣고 110℃에서 12 시간 동안 교반하여 분자량 6,500g/mol, 산가 95, 고형분 25.5% 의 아크릴계 알칼리 가용성 바인더 수지를 얻었다. The temperature of the polymer solution was increased to 80 ° C. again, 1 g of tetrabutylammonium bromide and 0.1 g of MEHQ, a thermal polymerization inhibitor, were stirred for 30 minutes, 12 g of glycidyl methacrylate was added thereto, and stirred at 110 ° C. for 12 hours. An acrylic alkali-soluble binder resin having a molecular weight of 6,500 g / mol, an acid value of 95 and a solid content of 25.5% was obtained.
[비교 합성예 2][Comparative Synthesis Example 2]
(알칼리 가용성 수지의 중합)(Polymerization of Alkali Soluble Resin)
스티렌 50g, 메타아크릴산 20g, 3-머켑토프로핀산 2g 을 300g의 3-메톡시부틸 아세테이트와 프로필렌 글리콜 모노메틸 에테르 아세테이트 5 : 5 혼합 용매에 혼합하고 질소 분위기 하에서 반응기의 온도를 60℃로 높였다. 혼합물의 온도가 60℃가 되었을 때 열중합 개시제인 AIBN 2.6g을 넣고 12시간 동안 교반하였다. 12시간 후, 중합 수율 95.5%, 분자량 6,000 g/mol, 고형분 25% 의 아크릴계 바인더 수지를 얻었다. 50 g of styrene, 20 g of methacrylic acid and 2 g of 3-mercetopropionic acid were mixed with 300 g of 3-methoxybutyl acetate and propylene glycol monomethyl ether acetate 5: 5 mixed solvent, and the temperature of the reactor was raised to 60 ° C. under a nitrogen atmosphere. When the temperature of the mixture reached 60 ° C., 2.6 g of AIBN, a thermal polymerization initiator, was added thereto, and the mixture was stirred for 12 hours. After 12 hours, an acrylic binder resin having a polymerization yield of 95.5%, a molecular weight of 6,000 g / mol and a solid content of 25% was obtained.
이 고분자 용액의 온도를 다시 80℃로 높인 후, 테트라부틸암모늄 브로마이드 1g 과 열중합 금지제인 MEHQ 0.1g을 넣고 30분간 교반한 후, 글리시딜 메타아크릴레이트 12g 을 넣고 110℃에서 12 시간 동안 교반하여 분자량 6,500g/mol, 산가 92, 고형분 25.9% 의 아크릴계 알칼리 가용성 바인더 수지를 얻었다. After raising the temperature of the polymer solution to 80 ° C. again, 1 g of tetrabutylammonium bromide and 0.1 g of MEHQ, a thermal polymerization inhibitor, were stirred for 30 minutes, and then 12 g of glycidyl methacrylate was added and stirred at 110 ° C. for 12 hours. To obtain an acrylic alkali-soluble binder resin having a molecular weight of 6,500 g / mol, an acid value of 92, and a solid content of 25.9%.
[실시예 1]Example 1
상기 합성예 2 에서 합성한 플루오렌계 바인더 수지 20 중량부를 카본 블랙 분산액 100 중량부, 광개시제인 CGI-242 5 중량부, 디펜타에리스리톨 헥사아크릴레이트 40 중량부, 용매인 프로필렌글리콜 모노메틸에테르 아세테이트 80 중량부를 혼합하여 3시간 정도 교반한 후, 감광성 수지 조성물을 준비하였다. 20 parts by weight of the fluorene-based binder resin synthesized in Synthesis Example 2, 100 parts by weight of a carbon black dispersion, 5 parts by weight of CGI-242 as a photoinitiator, 40 parts by weight of dipentaerythritol hexaacrylate, and propylene glycol monomethyl ether acetate as a solvent. After mixing a weight part and stirring for about 3 hours, the photosensitive resin composition was prepared.
[실시예 2][Example 2]
상기 합성예 3 에서 합성한 플루오렌계 바인더 수지 20 중량부를 상기 실시예 1에서 사용된 것과 동일한 조성으로 하여 혼합하고, 3시간 정도 교반한 후, 감광성 수지 조성물을 준비하였다. 20 parts by weight of the fluorene-based binder resin synthesized in Synthesis Example 3 was mixed in the same composition as used in Example 1, stirred for about 3 hours, and then a photosensitive resin composition was prepared.
[비교예 1]Comparative Example 1
상기 비교 합성예 1 에서 합성한 아크릴계 바인더 수지 20 중량부를 상기 실시예 1에서 사용된 것과 동일한 조성으로 하여 혼합하고, 3시간 정도 교반한 후, 감광성 수지 조성물을 준비하였다. 20 parts by weight of the acrylic binder resin synthesized in Comparative Synthesis Example 1 was mixed in the same composition as used in Example 1, stirred for about 3 hours, and then a photosensitive resin composition was prepared.
[비교예 2]Comparative Example 2
상기 비교 합성예 2 에서 합성한 아크릴계 바인더 수지 20 중량부를 상기 실시예 1에서 사용된 것과 동일한 조성으로 하여 혼합하고, 3시간 정도 교반한 후, 감광성 수지 조성물을 준비하였다. 20 parts by weight of the acrylic binder resin synthesized in Comparative Synthesis Example 2 was mixed in the same composition as used in Example 1, stirred for about 3 hours, and then a photosensitive resin composition was prepared.
[실험예][Experimental Example]
실시예 1, 실시예 2, 비교예 1 및 비교예 2 에서 제조한 각각의 감광성 수지 조성물 용액을 유리 기판 위에 스핀 코팅하고, 110℃에서 90초간 전열 처리하여 1.5㎛ 두께의 도막을 형성한 후, 이 도막 위에 포토마스크를 덮고 100mJ/cm2 의 에너지로 노광시킨 후, 25℃의 0.04% KOH 수용액으로 60초간 현상하였다. 현상 후, 230℃ 컨벡션 오븐에서 30분간 건조 과정을 거친 후, 패턴의 상태를 관찰하였다. After spin coating each of the photosensitive resin composition solutions prepared in Examples 1, 2, Comparative Example 1 and Comparative Example 2 onto a glass substrate and conducting heat transfer at 110 ° C. for 90 seconds to form a 1.5 μm thick coating film, The photomask was covered on this coating film and exposed to an energy of 100 mJ / cm 2 , followed by development for 60 seconds with a 0.04% KOH aqueous solution at 25 ° C. After development, after drying for 30 minutes in a 230 ℃ convection oven, the state of the pattern was observed.
상기 실험예에서 얻어진 각각의 패턴 상태를 광학 현미경으로 관찰하여 상용성 및 감도, NMP용액에 대한 내화학성을 측정하여 하기 표 1 과 같이 비교해보았다.Each pattern state obtained in the above experimental example was observed under an optical microscope, and the compatibility and sensitivity, and chemical resistance to the NMP solution were measured and compared as shown in Table 1 below.
상기 표 1에서 내화학성은 상기 실시예 및 비교 실시예에서 얻어진 각 기판을 NMP 용액에 40℃에서 30분간 담근 후 코팅막의 외관 변화를 관찰한 것으로 표기하였는데, 이때 외관 변화가 없는 것을 양호(ㅇ), 약간의 상태변화가 감지되는 것을 보통(△), 외관이 박리되거나 용제 색깔이 변질된 것을 불량(X)으로 표기한 것이다. In Table 1, the chemical resistance was indicated by immersing each substrate obtained in the Examples and Comparative Examples in an NMP solution at 40 ° C. for 30 minutes and then observing the appearance change of the coating film. In general, a slight state change is detected (△), the appearance is peeled off or the color of the solvent is marked as defective (X).
또한, 표 1에서 감도는 노광 및 현상 공정을 마친 후 남아있는 최소 픽셀의 크기이며, 상용성은 감광성 수지 조성물을 구성하는 다른 화합물과 혼합했을 때의 침전 발생 유무 및 혼합액의 투명도 등을 육안으로 관찰한 결과이다. In addition, the sensitivity in Table 1 is the size of the minimum pixel remaining after the exposure and development process, the compatibility is observed by visual observation of the occurrence of precipitation and the transparency of the mixed solution when mixed with other compounds constituting the photosensitive resin composition The result is.
상기 표 1의 결과에서 확인할 수 있는 바와 같이, 본 발명에 따른 플루오렌 그룹을 포함하는 알칼리 가용성 수지 중합체는 기존의 아크릴계 알칼리 가용성 수지 대비 동등 이상의 상용성을 갖으면서, 내화학성 및 감도가 우수하여 네가티브형 감광성 수지 조성물에 적용시 효과적이다. As can be seen from the results of Table 1, the alkali-soluble resin polymer containing a fluorene group according to the present invention has an equivalent or more compatibility compared to the conventional acrylic alkali-soluble resin, while having excellent chemical resistance and sensitivity, negative It is effective when applied to a type photosensitive resin composition.
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| KR101367253B1 (en) | 2010-10-13 | 2014-03-13 | 제일모직 주식회사 | Photosensitive resin composition and black matrix using the same |
| KR101486560B1 (en) | 2010-12-10 | 2015-01-27 | 제일모직 주식회사 | Photosensitive resin composition and black matrix using the same |
| KR101373990B1 (en) * | 2010-12-21 | 2014-03-12 | 주식회사 엘지화학 | Alkali soluble resin polymer comprising fluorene group, method for preparing the same and photo-sensitive resin composition comprising the polymer |
| KR101453769B1 (en) | 2010-12-24 | 2014-10-22 | 제일모직 주식회사 | Photosensitive resin composition and color filter using the same |
| KR20140076320A (en) | 2012-12-12 | 2014-06-20 | 제일모직주식회사 | Photosensitive resin composition and black spacer using the same |
| JP6059754B2 (en) * | 2014-03-20 | 2017-01-11 | 富士フイルム株式会社 | Composition, curable composition, transparent film, solid-state imaging device, and display device |
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