JP6854147B2 - Resin for photo spacers, resin composition for photo spacers, photo spacers and color filters - Google Patents
Resin for photo spacers, resin composition for photo spacers, photo spacers and color filters Download PDFInfo
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- JP6854147B2 JP6854147B2 JP2017028191A JP2017028191A JP6854147B2 JP 6854147 B2 JP6854147 B2 JP 6854147B2 JP 2017028191 A JP2017028191 A JP 2017028191A JP 2017028191 A JP2017028191 A JP 2017028191A JP 6854147 B2 JP6854147 B2 JP 6854147B2
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- JP
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- Prior art keywords
- resin
- photo spacer
- group
- weight
- monomer
- Prior art date
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- 125000006850 spacer group Chemical group 0.000 title claims description 101
- 229920005989 resin Polymers 0.000 title claims description 66
- 239000011347 resin Substances 0.000 title claims description 66
- 239000011342 resin composition Substances 0.000 title claims description 39
- 239000000178 monomer Substances 0.000 claims description 72
- 229920001296 polysiloxane Polymers 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 38
- 239000000203 mixture Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- -1 acrylate compound Chemical class 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000004973 liquid crystal related substance Substances 0.000 description 20
- 238000007664 blowing Methods 0.000 description 18
- 239000000758 substrate Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 12
- 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 12
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 12
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 8
- 150000008065 acid anhydrides Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- NRTLTGGGUQIRRT-UHFFFAOYSA-N triethylazanium;bromide Chemical compound [Br-].CC[NH+](CC)CC NRTLTGGGUQIRRT-UHFFFAOYSA-N 0.000 description 5
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 125000005395 methacrylic acid group Chemical group 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229940014800 succinic anhydride Drugs 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 2
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 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 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- 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
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 description 1
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- UIZDKHDPZRCOBN-UHFFFAOYSA-N 3-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCC1=CC(=O)NC1=O UIZDKHDPZRCOBN-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical compound CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-UHFFFAOYSA-N 0.000 description 1
- PTKHNBWCIHXVFS-UHFFFAOYSA-N 4-[2-methyl-1-(4-methylsulfanylphenyl)propan-2-yl]morpholine Chemical compound C1=CC(SC)=CC=C1CC(C)(C)N1CCOCC1 PTKHNBWCIHXVFS-UHFFFAOYSA-N 0.000 description 1
- 102100040440 Adenylate kinase isoenzyme 5 Human genes 0.000 description 1
- 101710168711 Adenylate kinase isoenzyme 5 Proteins 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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Description
本発明は、フォトスペーサー用樹脂、フォトスペーサー用樹脂組成物、フォトスペーサー及びカラーフィルタに関する。 The present invention relates to a resin for a photo spacer, a resin composition for a photo spacer, a photo spacer, and a color filter.
従来、液晶表示装置においては、カラーフィルタ側基板と薄膜トランジスタ（ＴＦＴ）側基板の間に挟持される液晶層の厚みを保持するために、フォトスペーサーが用いられている。 Conventionally, in a liquid crystal display device, a photo spacer is used to maintain the thickness of the liquid crystal layer sandwiched between the color filter side substrate and the thin film transistor (TFT) side substrate.
フォトスペーサーは一般に、感光性樹脂組成物を基板に塗布し、乾燥した後に所定の微細パターンを有するフォトマスクを通した光で露光し、現像することにより形成する。しかし、従来の感光性樹脂を用いて形成されたフォトスペーサーは、塑性変形量が大きく、セル組み立て工程での圧着時に、フォトスペーサーの高さにバラツキを生じるという問題があった。 Photospacers are generally formed by applying a photosensitive resin composition to a substrate, drying it, exposing it to light through a photomask having a predetermined fine pattern, and developing it. However, the photo spacer formed by using the conventional photosensitive resin has a large amount of plastic deformation, and has a problem that the height of the photo spacer varies during crimping in the cell assembly process.
この問題を解決するために、フォトスペーサーの硬さを増加させると、低温下での液晶の収縮にフォトスペーサーが追従できず、気泡が生じて、色抜け、色ムラ等の表示不良が起こるという問題が生じる。 If the hardness of the photo spacer is increased in order to solve this problem, the photo spacer cannot follow the shrinkage of the liquid crystal at a low temperature, and bubbles are generated, resulting in display defects such as color loss and color unevenness. Problems arise.
例えば、特許文献１では、低温発泡を生ずることなく、重力不良による色ムラの発生を効果的に抑制できるカラムスペーサを製造することを目的として、カプロラクトン変性された３官能以上の（メタ）アクリレート化合物、側鎖に（メタ）アクリル基とカルボキシル基とを有するアルカリ可溶性（メタ）アクリル共重合体、及び、光反応開始剤を含有するカラムスペーサ用硬化性樹脂組成物が提案されている。 For example, in Patent Document 1, a caprolactone-modified trifunctional or higher functional (meth) acrylate compound is used for the purpose of producing a column spacer capable of effectively suppressing the occurrence of color unevenness due to poor gravity without causing low-temperature foaming. , An alkali-soluble (meth) acrylic copolymer having a (meth) acrylic group and a carboxyl group in the side chain, and a curable resin composition for a column spacer containing a photoreaction initiator have been proposed.
また、近年、液晶表示装置のマザーガラスが大きくなるに従い、基板間に液晶を収容する方法として、従来の液晶流入方法（真空吸引方式）に代わって滴下方式（ＯＤＦ：One Drop Fill）が提案されている。ＯＤＦ方式では、所定量の液晶を滴下した後、基板で挟持することによって基板間に液晶を収容するため、従来の真空吸引方式に比べ、工程数および工程時間の短縮が可能である。 Further, in recent years, as the size of the mother glass of a liquid crystal display device has increased, a drop method (ODF: One Drop Fill) has been proposed as a method for accommodating liquid crystal between substrates, instead of the conventional liquid crystal inflow method (vacuum suction method). ing. In the ODF method, after dropping a predetermined amount of liquid crystal, the liquid crystal is accommodated between the substrates by sandwiching it between the substrates, so that the number of steps and the process time can be shortened as compared with the conventional vacuum suction method.
しかし、ＯＤＦ方式の中には液晶を滴下し、基板間に液晶を挟持した後に、真空引きまたは機械的圧力をかけて基板間から気泡を追い出す工程を行う場合がある。この時、フォトスペーサーに圧力をかけて気泡を追い出すことになるが、その際にフォトスペーサーの変形量が小さいと液晶パネル中に気泡が残るといった不良が発生する。そのため、フォトスペーサーには、小さな圧力に対しても大きく変形することが求められる。 However, in the ODF method, a step of dropping liquid crystals, sandwiching the liquid crystals between the substrates, and then applying vacuum or mechanical pressure to expel air bubbles from the substrates may be performed. At this time, pressure is applied to the photo spacer to expel air bubbles, but if the amount of deformation of the photo spacer is small at that time, defects such as air bubbles remaining in the liquid crystal panel occur. Therefore, the photo spacer is required to be greatly deformed even with a small pressure.
一方、液晶パネルを形成した後の問題として、液晶パネル表面を指で押すなどして外部から力または衝撃が液晶パネルに加わった際にフォトスペーサーが潰れてしまうと、部分的にセルギャップが小さくなり、表示不良となることがある。そのため、フォトスペーサーには、復元率が大きく、塑性変形量が小さいことが求められる。 On the other hand, as a problem after forming the liquid crystal panel, if the photo spacer is crushed when an external force or impact is applied to the liquid crystal panel by pressing the surface of the liquid crystal panel with a finger, the cell gap is partially small. As a result, the display may be defective. Therefore, the photo spacer is required to have a large restoration rate and a small amount of plastic deformation.
例えば、特許文献２では、ガラス基板に対する密着性や弾性回復力に優れた柱状スペーサーを提供することを目的として、酸基を導入し得るモノマーを必須モノマーとして含むモノマー成分を、ポリシロキサン結合を有し、かつ、チオール基を２個以上有するメルカプト変性ポリシロキサンの存在下で重合して得られる酸基含有ポリマーの酸基に、ラジカル重合性不飽和二重結合と酸基と反応し得る官能基とを有する化合物を反応させることによって得られる感光性ポリマーと、多官能モノマーと、光重合開始剤とを有するアルカリ可溶型硬化性樹脂組成物が提案されている。 For example, in Patent Document 2, for the purpose of providing a columnar spacer having excellent adhesion to a glass substrate and elastic recovery power, a monomer component containing a monomer capable of introducing an acid group as an essential monomer has a polysiloxane bond. A functional group capable of reacting with a radically polymerizable unsaturated double bond and an acid group on the acid group of the acid group-containing polymer obtained by polymerization in the presence of a mercapto-modified polysiloxane having two or more thiol groups. An alkali-soluble curable resin composition having a photosensitive polymer obtained by reacting a compound having the above, a polyfunctional monomer, and a photopolymerization initiator has been proposed.
しかし、小さな圧力で大きく変形する柔軟なフォトスペーサーは復元性が悪く、一方、塑性変形量が小さく、復元性に優れるフォトスペーサーは柔軟性に欠けるため、従来のフォトスペーサーでは高柔軟性と高復元性とを両立することは困難であった。 However, a flexible photo spacer that deforms greatly with a small pressure has poor resilience, while a photo spacer that has a small amount of plastic deformation and excellent resilience lacks flexibility. It was difficult to achieve both sex.
本発明は、高柔軟性と高復元性とを両立したフォトスペーサー、当該フォトスペーサーを形成するためのフォトスペーサー用樹脂及びフォトスペーサー用樹脂組成物、並びに当該フォトスペーサーを有するカラーフィルタを提供することを目的とする。 The present invention provides a photo spacer having both high flexibility and high resilience, a resin for a photo spacer for forming the photo spacer, a resin composition for the photo spacer, and a color filter having the photo spacer. With the goal.
本発明者らは、前記課題を解決すべく鋭意検討を重ねた結果、フォトスペーサーの形成樹脂として、以下に示す樹脂を用いることにより上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors have found that the above object can be achieved by using the following resin as the resin for forming the photospacer, and have completed the present invention. ..
本発明は、下記一般式（１）で表されるシリコーン含有モノマーに由来するモノマー単位Ａを含み、かつ側鎖に酸基を有するフォトスペーサー用樹脂、に関する。
前記モノマー単位Ａの含有量は、全モノマー単位中に５〜８０重量％であることが好ましい。前記モノマー単位Ａの含有量が５重量％未満の場合には、フォトスペーサーの柔軟性が十分に発現しない傾向にある。一方、前記モノマー単位Ａの含有量が８０重量％を超えると、フォトスペーサーのヘイズ（表面粗さ）が大きくなる傾向にある。 The content of the monomer unit A is preferably 5 to 80% by weight in all the monomer units. When the content of the monomer unit A is less than 5% by weight, the flexibility of the photo spacer tends not to be sufficiently exhibited. On the other hand, when the content of the monomer unit A exceeds 80% by weight, the haze (surface roughness) of the photo spacer tends to increase.
前記シリコーン含有モノマーの重量平均分子量は、２０００〜８０００であることが好ましい。前記シリコーン含有モノマーの重量平均分子量が２０００未満の場合には、当該フォトスペーサー用樹脂を含む組成物を基板上に塗布した際にハジキが発生しやすくなり、均一で精度の高いフォトスペーサーを形成することが難しくなる。一方、前記シリコーン含有モノマーの重量平均分子量が８０００を超えると、重合して得られる樹脂の溶解性が低下して析出するため、均一に溶解したフォトスペーサー用樹脂組成物を調製することが難しくなる。 The weight average molecular weight of the silicone-containing monomer is preferably 2000 to 8000. When the weight average molecular weight of the silicone-containing monomer is less than 2000, repelling is likely to occur when the composition containing the photospacer resin is applied onto the substrate, and a uniform and highly accurate photospacer is formed. It becomes difficult. On the other hand, when the weight average molecular weight of the silicone-containing monomer exceeds 8000, the solubility of the resin obtained by polymerization is lowered and precipitated, so that it becomes difficult to prepare a uniformly dissolved resin composition for a photospacer. ..
前記フォトスペーサー用樹脂は、さらに下記一般式（２）で表されるジオキソラン含有モノマーに由来するモノマー単位Ｂを含むことが好ましい。
前記ジオキソラン含有モノマーを共重合モノマーとして用いることにより、得られるフォトスペーサー用樹脂の溶解性が向上するため、高濃度でフォトスペーサー用樹脂を調製でき、しかも反応時間を大幅に短縮することができる。 By using the dioxolane-containing monomer as the copolymerization monomer, the solubility of the obtained photospacer resin is improved, so that the photospacer resin can be prepared at a high concentration, and the reaction time can be significantly shortened.
前記モノマー単位Ｂの含有量は、全モノマー単位中に２〜３０重量％であることが好ましい。前記モノマー単位Ｂの含有量が２重量％未満の場合には、上記効果が得られ難い傾向にある。一方、前記モノマー単位Ｂの含有量が３０重量％を超えると、得られるフォトスペーサーの復元性が低下する傾向にある。 The content of the monomer unit B is preferably 2 to 30% by weight in all the monomer units. When the content of the monomer unit B is less than 2% by weight, it tends to be difficult to obtain the above effect. On the other hand, when the content of the monomer unit B exceeds 30% by weight, the resilience of the obtained photo spacer tends to decrease.
前記フォトスペーサー用樹脂の重量平均分子量は、５０００〜１０００００であることが好ましい。前記フォトスペーサー用樹脂の重量平均分子量が５０００未満の場合には、得られるフォトスペーサーの柔軟性が低下する傾向にある。一方、前記フォトスペーサー用樹脂の重量平均分子量が１０００００を超えると、フォトスペーサー用樹脂組成物の現像性が悪くなる傾向にある。 The weight average molecular weight of the photospacer resin is preferably 5000 to 100,000. When the weight average molecular weight of the photo spacer resin is less than 5000, the flexibility of the obtained photo spacer tends to decrease. On the other hand, when the weight average molecular weight of the photo spacer resin exceeds 100,000, the developability of the photo spacer resin composition tends to deteriorate.
また、本発明は、前記フォトスペーサー用樹脂、多官能モノマー、及び光重合開始剤を含有するフォトスペーサー用樹脂組成物、に関する。 The present invention also relates to a resin composition for a photospacer containing the resin for a photospacer, a polyfunctional monomer, and a photopolymerization initiator.
前記フォトスペーサー用樹脂組成物の全固形分中における前記モノマー単位Ａの含有量は、３〜２０重量％であることが好ましい。前記モノマー単位Ａの含有量が３重量％未満の場合には、得られるフォトスペーサーの柔軟性が低下する傾向にある。一方、前記モノマー単位Ａの含有量が２０重量％を超えると、得られるフォトスペーサーの復元性が低下する傾向にある。 The content of the monomer unit A in the total solid content of the resin composition for a photospacer is preferably 3 to 20% by weight. When the content of the monomer unit A is less than 3% by weight, the flexibility of the obtained photo spacer tends to decrease. On the other hand, when the content of the monomer unit A exceeds 20% by weight, the resilience of the obtained photo spacer tends to decrease.
また、本発明は、前記フォトスペーサー用樹脂組成物を硬化して得られるフォトスペーサー、及び当該フォトスペーサーを有するカラーフィルタ、に関する。 The present invention also relates to a photo spacer obtained by curing the resin composition for a photo spacer, and a color filter having the photo spacer.
本発明のフォトスペーサーは、高柔軟性と高復元性とを両立した、従来にない特性を有するものである。当該フォトスペーサーを用いれば、液晶パネル作製時に液晶中に気泡が残存することを防止でき、また、外部から力や衝撃が液晶パネルに加わった場合でもセルギャップを均一に保つことができるため液晶表示装置の表示品質の劣化を防止できる。 The photospacer of the present invention has unprecedented characteristics that achieve both high flexibility and high resilience. By using the photo spacer, it is possible to prevent air bubbles from remaining in the liquid crystal when the liquid crystal panel is manufactured, and it is possible to keep the cell gap uniform even when a force or impact is applied to the liquid crystal panel from the outside, so that the liquid crystal display can be displayed. It is possible to prevent deterioration of the display quality of the device.
[フォトスペーサー用樹脂]
本発明のフォトスペーサー用樹脂は、下記一般式（１）で表されるシリコーン含有モノマーに由来するモノマー単位Ａを含み、かつ側鎖に酸基を有する。
The resin for a photo spacer of the present invention contains a monomer unit A derived from a silicone-containing monomer represented by the following general formula (1), and has an acid group in a side chain.
前記Ｒ２で表される炭素数２〜４のアルキレン基としては、例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、プロピレン基、エチルエチレン基等が挙げられる。 Examples of the alkylene group having 2 to 4 carbon atoms represented by R 2 include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a propylene group and an ethylethylene group.
前記Ｒ３で表される炭素数１〜４のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基等が挙げられる。 Examples of the alkyl group having 1 to 4 carbon atoms represented by R 3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and the like. ..
前記シリコーン含有モノマーとしては、例えば、α−ブチル−ω−（３−メタクリロキシプロピル）ポリジメチルシロキサン（例えばＪＮＣ株式会社製の「サイラプレーン（登録商標）ＦＭ−０７２１」（商品名））、ＪＮＣ株式会社製の「サイラプレーン（登録商標）ＦＭ−０７１１（商品名）」及び「サイラプレーン（登録商標）ＦＭ−０７２５（商品名）」、信越化学工業株式会社製の「Ｘ−２２−１７４ＡＳＸ（商品名）」、「Ｘ−２２−１７４ＤＸ（商品名）」、「Ｘ−２２−２４２６（商品名）」、「Ｘ−２２−２４０４（商品名）」、及び「ＫＦ−２０１２（商品名）」、東亞合成株式会社製の「ＡＫ−５（グレード）」及び「ＡＫ−３２（グレード）」等が挙げられる。これらシリコーン含有モノマーは単独で用いてもよく、２種以上を併用してもよい。 Examples of the silicone-containing monomer include α-butyl-ω- (3-methacryloxypropyl) polydimethylsiloxane (for example, “Silaplane® FM-0721” (trade name) manufactured by JNC Co., Ltd.) and JNC. "Silaplane (registered trademark) FM-0711 (trademark)" and "Silaplane (registered trademark) FM-0725 (trademark)" manufactured by Shin-Etsu Chemical Industry Co., Ltd., "X-22-174ASX" manufactured by Shin-Etsu Chemical Industry Co., Ltd. Product name) ”,“ X-22-174DX (product name) ”,“ X-22-2426 (product name) ”,“ X-22-2404 (product name) ”, and“ KF-22 (product name) , "AK-5 (grade)" and "AK-32 (grade)" manufactured by Toa Synthetic Co., Ltd. and the like. These silicone-containing monomers may be used alone or in combination of two or more.
前記シリコーン含有モノマーの重量平均分子量は特に制限されないが、２０００以上であることが好ましく、より好ましくは４０００以上であり、また、８０００以下であることが好ましく、より好ましくは６０００以下である。 The weight average molecular weight of the silicone-containing monomer is not particularly limited, but is preferably 2000 or more, more preferably 4000 or more, and preferably 8000 or less, more preferably 6000 or less.
前記フォトスペーサー用樹脂中の前記モノマー単位Ａの含有量は特に制限されないが、全モノマー単位中に５重量％以上であることが好ましく、より好ましくは８重量％以上であり、さらに好ましくは１２重量％以上であり、また、８０重量％以下であることが好ましく、より好ましくは６０重量％以下であり、さらに好ましくは４０重量％以下である。 The content of the monomer unit A in the photospacer resin is not particularly limited, but is preferably 5% by weight or more, more preferably 8% by weight or more, and further preferably 12% by weight in all the monomer units. % Or more, preferably 80% by weight or less, more preferably 60% by weight or less, still more preferably 40% by weight or less.
前記フォトスペーサー用樹脂は、さらに下記一般式（２）で表されるジオキソラン含有モノマーに由来するモノマー単位Ｂを含むことが好ましい。
前記Ｒ５で表される直鎖又は分岐鎖の炭素数１〜８のアルキレン基としては、例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、プロピレン基、エチルエチレン基、ブチレン基、ヘキシレン基、ヘプチレン基、オクチレン基等が挙げられる。 Examples of the alkylene group having 1 to 8 carbon atoms, straight-chain or branched-chain represented by R 5, for example, methylene group, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, butylene group, hexylene Examples include a group, a heptylene group, an octylene group and the like.
前記Ｒ６及びＲ７で表される直鎖、分岐鎖又は環状の炭素数１〜１８のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ステアリル基、シクロヘキシル基等が挙げられる。 Examples of the linear, branched or cyclic alkyl group having 1 to 18 carbon atoms represented by R 6 and R 7 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and t. -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, stearyl group, cyclohexyl group and the like can be mentioned.
前記ジオキソラン含有モノマーは単独で用いてもよく、２種以上を併用してもよい。前記ジオキソラン含有モノマーのうち、（２−メチル−２−エチル−１，３−ジオキソラン−４−イル）メチル（メタ）アクリレート、（２−メチル−２−イソブチル−１，３−ジオキソラン−４−イル）メチル（メタ）アクリレート、（シクロヘキサンスピロ−２−（１，３−ジオキソラン−４−イル））メチル（メタ）アクリレートを用いることが好ましい。 The dioxolane-containing monomer may be used alone or in combination of two or more. Among the dioxolane-containing monomers, (2-methyl-2-ethyl-1,3-dioxolane-4-yl) methyl (meth) acrylate and (2-methyl-2-isobutyl-1,3-dioxolan-4-yl) methyl (meth) acrylate ) Methyl (meth) acrylate, (cyclohexanespiro-2- (1,3-dioxolane-4-yl)) methyl (meth) acrylate is preferably used.
前記フォトスペーサー用樹脂中の前記モノマー単位Ｂの含有量は特に制限されないが、全モノマー単位中に２重量％以上であることが好ましく、より好ましくは４重量％以上であり、さらに好ましくは６重量％以上であり、また、３０重量％以下であることが好ましく、より好ましくは２５重量％以下であり、さらに好ましくは２０重量％以下である。 The content of the monomer unit B in the photospacer resin is not particularly limited, but is preferably 2% by weight or more, more preferably 4% by weight or more, and further preferably 6% by weight in all the monomer units. % Or more, preferably 30% by weight or less, more preferably 25% by weight or less, still more preferably 20% by weight or less.
前記フォトスペーサー用樹脂を形成するその他のモノマーとしては、例えば、（メタ）アクリル酸、２−（メタ）アクリロイルオキシエチルコハク酸、マレイン酸、及びイタコン酸等のカルボキシル基含有モノマー；無水マレイン酸、及び無水イタコン酸等のカルボン酸無水物基含有モノマー；メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、ラウリル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、及びグリシジル（メタ）アクリレート等のアルキル（メタ）アクリレート；シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、及びジシクロペンテニル（メタ）アクリレート等の脂環式（メタ）アクリレート等が挙げられる。また、スチレン、シクロヘキシルマレイミド、フェニルマレイミド、シクロヘキシルマレイミド、フェニルマレイミド、メチルマレイミド、エチルマレイミド、ｎ−ブチルマレイミド、及びラウリルマイレミド等を共重合モノマーとして用いてもよい。これらモノマーは、単独で用いてもよく、２種以上を併用してもよい。なお、本発明において、（メタ）アクリル酸とは、アクリル酸、メタクリル酸、又はそれらの混合物を意味する。同様に記載されている他の化合物についても同様の意味である。 Examples of other monomers forming the photospacer resin include carboxyl group-containing monomers such as (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, maleic acid, and itaconic acid; maleic anhydride, And carboxylic acid anhydride group-containing monomers such as itaconic anhydride; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, Alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate, and glycidyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclo Examples thereof include alicyclic (meth) acrylates such as pentenyl (meth) acrylates. Further, styrene, cyclohexylmaleimide, phenylmaleimide, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, laurylmaleimide and the like may be used as the copolymerization monomer. These monomers may be used alone or in combination of two or more. In the present invention, (meth) acrylic acid means acrylic acid, methacrylic acid, or a mixture thereof. The same meaning applies to other compounds described in the same manner.
前記フォトスペーサー用樹脂は、アルカリ現像性を付与するために側鎖に酸基を有する。前記フォトスペーサー用樹脂の側鎖に酸基を導入する方法は特に制限されず、公知の方法を採用でき、例えば、カルボキシル基含有モノマーやカルボン酸無水物基含有モノマーを共重合させる方法、（メタ）アクリル酸等のカルボキシル基含有モノマーを共重合させた重合体にグリシジル（メタ）アクリレート等のエポキシ基含有化合物を付加させる事により生成した水酸基に酸無水物を付加させる方法、及びグリシジル（メタ）アクリレート等のエポキシ基含有モノマーを共重合させた重合体に（メタ）アクリル酸等のカルボキシル基含有化合物を付加させる事により生成した水酸基に酸無水物を付加させる方法等が挙げられる。 The photospacer resin has an acid group in the side chain in order to impart alkali developability. The method of introducing an acid group into the side chain of the photospacer resin is not particularly limited, and a known method can be adopted. For example, a method of copolymerizing a carboxyl group-containing monomer or a carboxylic acid anhydride group-containing monomer, (meth ) A method of adding an acid anhydride to a hydroxyl group generated by adding an epoxy group-containing compound such as glycidyl (meth) acrylate to a polymer obtained by copolymerizing a carboxyl group-containing monomer such as acrylic acid, and glycidyl (meth). Examples thereof include a method of adding an acid anhydride to a hydroxyl group generated by adding a carboxyl group-containing compound such as (meth) acrylic acid to a polymer obtained by copolymerizing an epoxy group-containing monomer such as acrylate.
また、前記フォトスペーサー用樹脂の側鎖にエチレン性不飽和基を導入してもよい。前記フォトスペーサー用樹脂の側鎖にエチレン性不飽和基を導入する方法としては、例えば、グリシジル（メタ）アクリレート等のエポキシ基含有モノマーを共重合させた重合体に（メタ）アクリル酸等のエチレン性不飽和基とカルボキシル基とを有する化合物を付加する方法、（メタ）アクリル酸等のカルボキシル基含有モノマーを共重合させた重合体にグリシジル（メタ）アクリレート等のエチレン性不飽和基とエポキシ基とを有する化合物を付加する方法、及びヒドロキシエチル（メタ）アクリレート等のヒドロキシル基含有モノマーを共重合させた重合体に（メタ）アクリロイルオキシエチルイソシアネート等のエチレン性不飽和基とイソシアネート基とを有する化合物を付加する方法等が挙げられる。 Further, an ethylenically unsaturated group may be introduced into the side chain of the photospacer resin. As a method for introducing an ethylenically unsaturated group into the side chain of the photospacer resin, for example, ethylene such as (meth) acrylic acid is used in a polymer obtained by copolymerizing an epoxy group-containing monomer such as glycidyl (meth) acrylate. A method of adding a compound having a sex unsaturated group and a carboxyl group, an ethylenic unsaturated group such as glycidyl (meth) acrylate and an epoxy group in a polymer obtained by copolymerizing a carboxyl group-containing monomer such as (meth) acrylic acid. It has an ethylenically unsaturated group such as (meth) acryloyloxyethyl isocyanate and an isocyanate group in a polymer obtained by copolymerizing a hydroxyl group-containing monomer such as hydroxyethyl (meth) acrylate. Examples thereof include a method of adding a compound.
前記フォトスペーサー用樹脂の重量平均分子量は特に制限されないが、５０００以上であることが好ましく、より好ましくは１００００以上であり、さらに好ましくは１５０００以上であり、また、１０００００以下であることが好ましく、より好ましくは８００００以下であり、さらに好ましくは６００００以下である。 The weight average molecular weight of the photospacer resin is not particularly limited, but is preferably 5000 or more, more preferably 10000 or more, further preferably 15000 or more, and preferably 100,000 or less. It is preferably 80,000 or less, and more preferably 60,000 or less.
[フォトスペーサー用樹脂組成物]
本発明のフォトスペーサー用樹脂組成物は、前記フォトスペーサー用樹脂、多官能モノマー、及び光重合開始剤を含有する。
[Resin composition for photo spacer]
The resin composition for a photospacer of the present invention contains the resin for a photospacer, a polyfunctional monomer, and a photopolymerization initiator.
多官能モノマーを配合することにより、光重合やポストベークの際に、多官能モノマー同士が反応して、あるいは多官能モノマーと前記フォトスペーサー用樹脂中の二重結合とが反応して、三次元架橋された硬化膜が形成される。 By blending the polyfunctional monomer, the polyfunctional monomers react with each other during photopolymerization or post-baking, or the polyfunctional monomer reacts with the double bond in the photospacer resin to be three-dimensional. A crosslinked cured film is formed.
多官能モノマーは特に制限されず、例えば、ジビニルベンゼン、ジアリルフタレート、及びジアリルベンゼンホスホネート等の多官能芳香族ビニル系モノマー；（ジ）エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、及びトリス（ヒドロキシエチル）イソシアヌレートのトリ（メタ）アクリレート等の多官能（メタ）アクリレート等が挙げられる。これらのうち、官能基数の多い（ジ）ペンタエリスリトールテトラ（メタ）アクリレート、（ジ）ペンタエリスリトールペンタ（メタ）アクリレート、（ジ）ペンタエリスリトールヘキサ（メタ）アクリレート、及びトリス（ヒドロキシエチル）イソシアヌレートのトリ（メタ）アクリレートが好ましい。これら多官能モノマーは、単独で用いてもよく、２種以上を併用してもよい。 The polyfunctional monomer is not particularly limited, and for example, a polyfunctional aromatic vinyl-based monomer such as divinylbenzene, diallylphthalate, and diallylbenzenephosphonate; (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Trimethylol Propane Di (meth) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Di (Meta) Acrylate , Dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tris (hydroxyethyl) isocyanurate tri (meth). Examples thereof include polyfunctional (meth) acrylates such as acrylates. Of these, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol penta (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, and tris (hydroxyethyl) isocyanurate having a large number of functional groups. Tri (meth) acrylate is preferred. These polyfunctional monomers may be used alone or in combination of two or more.
多官能モノマーの含有量は、前記フォトスペーサー用樹脂１００重量部に対して４０重量部以上であることが好ましく、より好ましくは６０重量部以上であり、さらに好ましくは８０重量部以上であり、また、２５０重量部以下であることが好ましく、より好ましくは２００重量部以下であり、さらに好ましくは１６０重量部以下である。多官能モノマーの含有量が４０重量部未満の場合には、充分な架橋効果が得られず、本発明の効果が十分に得られない可能性がある。一方、多官能モノマーの含有量が２５０重量部を超えると、フォトスペーサー用樹脂組成物の現像性が悪くなる傾向にある。 The content of the polyfunctional monomer is preferably 40 parts by weight or more, more preferably 60 parts by weight or more, still more preferably 80 parts by weight or more, based on 100 parts by weight of the photospacer resin. , 250 parts by weight or less, more preferably 200 parts by weight or less, still more preferably 160 parts by weight or less. When the content of the polyfunctional monomer is less than 40 parts by weight, a sufficient cross-linking effect cannot be obtained, and the effect of the present invention may not be sufficiently obtained. On the other hand, when the content of the polyfunctional monomer exceeds 250 parts by weight, the developability of the photospacer resin composition tends to deteriorate.
光重合開始剤は特に制限されず、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル等のベンゾインとそのアルキルエーテル類；アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン等のアセトフェノン類；２−メチルアントラキノン、２−アミルアントラキノン、２−ｔ−ブチルアントラキノン、１−クロロアントラキノン等のアントラキノン類；２，４−ジメチルチオキサントン、２，４−ジイソプロピルチオキサントン、２−クロロチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフェノン等のベンゾフェノン類；２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オンや２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１；アシルホスフィンオキサイド類およびキサントン類等が挙げられる。これら光重合開始剤は、単独で用いてもよく、２種以上を併用してもよい。 The photopolymerization initiator is not particularly limited, and for example, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and its alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and the like. Acetophenones; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and the like. Thioxanthones; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone; 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides, xanthones and the like can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more.
光重合開始剤の含有量は特に制限されないが、前記フォトスペーサー用樹脂１００重量部に対して、１重量部以上であることが好ましく、より好ましくは３重量部以上であり、さらに好ましくは５重量部以上であり、また、２０重量部以下であることが好ましく、より好ましくは１５重量部以下であり、さらに好ましくは１０重量部以下である。 The content of the photopolymerization initiator is not particularly limited, but is preferably 1 part by weight or more, more preferably 3 parts by weight or more, still more preferably 5 parts by weight, based on 100 parts by weight of the photospacer resin. It is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and further preferably 10 parts by weight or less.
前記フォトスペーサー用樹脂組成物には、光重合開始助剤を添加してもよい。光重合開始助剤としては、例えば、１，３，５−トリス（３−メルカプトプロピオニルオキシエチル）−イソシアヌレート、１，３，５−トリス（３−メルカプトブチルオキシエチル）−イソシアヌレート（昭和電工社製、カレンズＭＴ（登録商標）ＮＲ１）、トリメチロールプロパントリス（３−メルカプトプロピオネート）等の３官能チオール化合物；ペンタエリスリトールテトラキス（３−メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３−メルカプトブチレート）（昭和電工社製、カレンズＭＴ（登録商標）ＰＥＩ）等の４官能チオール化合物；ジペンタエリスリトールヘキサキス（３−プロピオネート）等の６官能チオール化合物等の多官能チオールが挙げられる。これら光重合開始助剤は、単独で用いてもよく、２種以上を併用してもよい。 A photopolymerization initiator may be added to the resin composition for a photospacer. Examples of the photopolymerization initiator include 1,3,5-tris (3-mercaptopropionyloxyethyl) -isocyanurate and 1,3,5-tris (3-mercaptobutyloxyethyl) -isocyanurate (Showa Denko). Trifunctional thiol compounds such as Karenz MT (registered trademark) NR1) and trimethylolpropanthris (3-mercaptopropionate); pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto) Butyrate) (manufactured by Showa Denko, Inc., Karenz MT (registered trademark) PEI) and other tetrafunctional thiol compounds; and polyfunctional thiols such as dipentaerythritol hexakis (3-propionate) and other hexafunctional thiol compounds can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more.
前記フォトスペーサー用樹脂組成物には、熱重合開始剤を添加してもよい。熱重合開始剤としては、例えば、クメンハイドロパーオキサイド、ジイソプロピルベンゼンパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ラウリルパーオキサイド、ベンゾイルパーオキサイド、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシ−２−エチルヘキサノエート、ｔ−アミルパーオキシ−２−エチルヘキサノエート等の有機過酸化物；２，２’−アゾビス（イソブチロニトリル）、１，１’−アゾビス（シクロヘキサンカルボニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、ジメチル２，２’−アゾビス（２−メチルプロピオネート）等のアゾ化合物等が挙げられる。これら熱重合開始剤は、単独で用いてもよく、２種以上を併用してもよい。 A thermal polymerization initiator may be added to the resin composition for a photospacer. Examples of the thermal polymerization initiator include cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-butylperoxy-2. Organic peroxides such as -ethylhexanoate, t-amylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), Examples thereof include azo compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis (2-methylpropionate). These thermal polymerization initiators may be used alone or in combination of two or more.
前記フォトスペーサー用樹脂組成物には、不飽和ポリエステル、エポキシアクリレート、ウレタンアクリレート、ポリエステルアクリレート等のラジカル重合性オリゴマー；エポキシ樹脂等の硬化性樹脂を添加してもよい。 A radically polymerizable oligomer such as unsaturated polyester, epoxy acrylate, urethane acrylate, or polyester acrylate; or a curable resin such as epoxy resin may be added to the resin composition for a photospacer.
前記フォトスペーサー用樹脂組成物は、溶媒を含有していてもよい。溶媒としては、例えば、テトラヒドロフラン、ジオキサン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル等のエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、３−メトキシブチルアセテート等のエステル類；メタノール、エタノール、イソプロパノール、ｎ−ブタノール、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等のアルコール類；トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類；クロロホルム、ジメチルスルホキシド等が挙げられる。これら溶媒は、単独で用いてもよく、２種以上を併用してもよい。なお、溶媒の含有量は、樹脂組成物を使用する際の最適粘度に応じて適宜設定すればよい。 The resin composition for a photo spacer may contain a solvent. Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxy. Esters such as butyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform, dimethyl sulfoxide and the like Can be mentioned. These solvents may be used alone or in combination of two or more. The content of the solvent may be appropriately set according to the optimum viscosity when the resin composition is used.
前記フォトスペーサー用樹脂組成物は、本発明の効果を損なわない範囲で、水酸化アルミニウム、タルク、クレー、硫酸バリウム等の充填材、染料、顔料、消泡剤、カップリング剤、レベリング剤、増感剤、離型剤、滑剤、可塑剤、酸化防止剤、紫外線吸収剤、難燃剤、重合抑制剤、増粘剤、及び分散剤等の公知の添加剤を含有していてもよい。 The resin composition for photo spacers contains fillers such as aluminum hydroxide, talc, clay, and barium sulfate, dyes, pigments, defoaming agents, coupling agents, leveling agents, and more, as long as the effects of the present invention are not impaired. It may contain known additives such as sensitizers, mold release agents, talc, plasticizers, antioxidants, UV absorbers, flame retardants, polymerization inhibitors, thickeners, and dispersants.
前記フォトスペーサー用樹脂組成物の全固形分中における前記モノマー単位Ａの含有量は、３重量％以上であることが好ましく、より好ましくは４重量％以上であり、さらに好ましくは５重量％以上であり、また、２０重量％以下であることが好ましく、より好ましくは１７重量％以下であり、さらに好ましくは１５重量％以下である。 The content of the monomer unit A in the total solid content of the resin composition for a photospacer is preferably 3% by weight or more, more preferably 4% by weight or more, still more preferably 5% by weight or more. Yes, and it is preferably 20% by weight or less, more preferably 17% by weight or less, and further preferably 15% by weight or less.
[フォトスペーサー]
本発明のフォトスペーサーの形成方法は特に制限されず、公知の方法で形成することができる。本発明のフォトスペーサーは、例えば、前記フォトスペーサー用樹脂組成物を、ガラス又は透明プラスチックフィルム等の基板に塗布し、乾燥して塗膜を形成し、次いで、フォトリソグラフィーにより形成することができる。フォトリソグラフィーにおいては、例えば、塗膜上にフォトマスクを配置し、紫外線を照射することにより塗膜を光硬化させ、紫外線照射後の塗膜にアルカリ水溶液を散布し、未露光部を溶解、除去して残った露光部を水洗して現像することにより、フォトスペーサーを形成する。その後、ポストベークを行ってもよい。
[Photo spacer]
The method for forming the photo spacer of the present invention is not particularly limited, and the photo spacer can be formed by a known method. The photospacer of the present invention can be formed, for example, by applying the resin composition for a photospacer to a substrate such as glass or a transparent plastic film and drying to form a coating film, and then by photolithography. In photolithography, for example, a photomask is placed on a coating film, the coating film is photocured by irradiating with ultraviolet rays, and an alkaline aqueous solution is sprayed on the coating film after irradiation with ultraviolet rays to dissolve and remove unexposed areas. The remaining exposed portion is washed with water and developed to form a photospacer. After that, post-baking may be performed.
前記フォトスペーサーの形状は特に制限されないが、例えば、円柱状、角柱状、円錐台形状、角錐台形状等が挙げられる。 The shape of the photo spacer is not particularly limited, and examples thereof include a columnar shape, a prismatic shape, a truncated cone shape, and a truncated cone shape.
前記フォトスペーサーの大きさは特に制限されないが、例えば、上底径は５〜１５μｍ程度であり、下底径は７〜２０μｍ程度であり、高さは液晶セルのセルギャップに応じて適宜設定すればよい。 The size of the photo spacer is not particularly limited, but for example, the upper bottom diameter is about 5 to 15 μm, the lower bottom diameter is about 7 to 20 μm, and the height is appropriately set according to the cell gap of the liquid crystal cell. Just do it.
前記フォトスペーサーは、２０ｍＮの荷重を負荷した時の変形量が０．６μｍ以上であることが好ましく、より好ましくは０．６５μｍ以上であり、さらに好ましくは０．７μｍ以上である。 The amount of deformation of the photo spacer when a load of 20 mN is applied is preferably 0.6 μm or more, more preferably 0.65 μm or more, and further preferably 0.7 μm or more.
また、前記フォトスペーサーは、復元率が７０％以上であることが好ましく、より好ましくは７２％以上であり、さらに好ましくは７５％以上である。なお、復元率の測定方法は実施例の記載による。 Further, the photo spacer preferably has a restoration rate of 70% or more, more preferably 72% or more, and further preferably 75% or more. The method for measuring the restoration rate is as described in Examples.
[カラーフィルタ]
本発明のカラーフィルタは、前記フォトスペーサーを有するものであればその他は特に制限されない。本発明のカラーフィルタは、例えば、透明基板上に、ブラックマトリックス、赤色画素、緑色画素、及び青色画素からなる着色層が設けられ、その上に透明導電層が設けられ、ブラックマトリックスの所定の位置に前記フォトスペーサーが設けられた構造を有する。本発明のカラーフィルタは、公知の方法により製造することができる。
[Color filter]
The color filter of the present invention is not particularly limited as long as it has the photo spacer. In the color filter of the present invention, for example, a colored layer composed of a black matrix, red pixels, green pixels, and blue pixels is provided on a transparent substrate, and a transparent conductive layer is provided on the colored layer, and a predetermined position of the black matrix is provided. Has a structure in which the photo spacer is provided. The color filter of the present invention can be produced by a known method.
以下に実施例をあげて本発明を説明するが、本発明はこれら実施例によりなんら限定されるものではない。 The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１
[フォトスペーサー用樹脂の合成]
片末端メタクリルシリコーン（信越化学工業株式会社製、ＫＦ―２０１２、Ｍｗ５０００）８．９ｇ、グリシジルメタクリレート（ＧＭＡ）１０ｇ、及び2,2'-アゾビス(2,4-ジメチルバレロニトリル)（ＡＤＶＮ）０．６ｇをプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＡｃ）１０７．１ｇに溶解させて窒素を吹き込みながら反応温度８０℃にて７時間反応させた。次にアクリル酸５．１ｇ、メトキノン０．１ｇ、及びトリエチルアンモニウムブロマイド０．１ｇを加え、空気を吹き込みながら反応温度９０℃で４８時間反応させた。４８時間後に酸価滴定を行い、アクリル酸由来のカルボン酸が消失していることを確認した。次に2-アクリロイルオキシエチルイソシアナート（昭和電工社製、カレンズＡＯＩ）７．４ｇを加え、空気を吹き込みながら反応温度６５℃で６時間反応させた。６時間後にＩＲ分析を行い、イソシアナート基の２２７０ｃｍ−１ピークが消失していることを確認した。最後に無水コハク酸を１．４ｇ加え、空気を吹き込みながら８０℃で４時間反応させて固形分濃度３０．６重量％の淡黄色透明のフォトスペーサー用樹脂溶液（１）を得た。４時間後ＩＲ分析を行い、酸無水物由来の１７８０ｃｍ−１ピークが消失していることを確認した。ＧＰＣにて分子量測定した結果、フォトスペーサー用樹脂のＭｗは３０，０００であり、フォトスペーサー用樹脂中のシリコーン含有量は２７．１重量％であった。なお、分子量測定は、ゲルパーミエイションクロマトグラフィー（東ソー(株)製、品番:HLC-8120、カラム：G-5000HXLおよびG-3000HXLの２連結、検出器：RI、移動相：テトラヒドロフラン）にて行った。
Example 1
[Synthesis of resin for photo spacer]
One-ended methacrylic silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KF-2012, Mw5000) 8.9 g, glycidyl methacrylate (GMA) 10 g, and 2,2'-azobis (2,4-dimethylvaleronitrile) (ADVN) 0. 6 g was dissolved in 107.1 g of propylene glycol monomethyl ether acetate (PGMAc), and the reaction was carried out at a reaction temperature of 80 ° C. for 7 hours while blowing nitrogen. Next, 5.1 g of acrylic acid, 0.1 g of methquinone, and 0.1 g of triethylammonium bromide were added, and the mixture was reacted at a reaction temperature of 90 ° C. for 48 hours while blowing air. Acid value titration was performed 48 hours later, and it was confirmed that the carboxylic acid derived from acrylic acid had disappeared. Next, 7.4 g of 2-acryloyloxyethyl isocyanate (Kalens AOI manufactured by Showa Denko KK) was added, and the mixture was reacted at a reaction temperature of 65 ° C. for 6 hours while blowing air. After 6 hours, IR analysis was performed, and it was confirmed that the 2270 cm-1 peak of the isocyanate group had disappeared. Finally, 1.4 g of succinic anhydride was added and reacted at 80 ° C. for 4 hours while blowing air to obtain a pale yellow transparent resin solution (1) for a photospacer having a solid content concentration of 30.6% by weight. After 4 hours, IR analysis was performed, and it was confirmed that the 1780 cm-1 peak derived from the acid anhydride had disappeared. As a result of measuring the molecular weight with GPC, the Mw of the photo spacer resin was 30,000, and the silicone content in the photo spacer resin was 27.1% by weight. The molecular weight is measured by gel permeation chromatography (manufactured by Tosoh Corporation, product number: HLC-8120, column: G-5000HXL and G-3000HXL, detector: RI, mobile phase: tetrahydrofuran). went.
[フォトスペーサー用樹脂組成物の調製]
フォトスペーサー用樹脂溶液（１）１６．３ｇ、ジペンタエリスリトールヘキサアクリレート（日本化薬株式会社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）７．５ｇ、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オン（ＢＡＳＦ社製、Ｉｒｇａｃｕｒｅ９０７）０．３ｇ、２，４−ジエチルチオキサテン−９−オン（ＬＡＭＢＳＯＮ、Ｓｐｅｅｄｃｕｒｅ ＤＥＴＸ）０．１ｇ、及びＰＧＭＡｃ１８．７ｇを加え、組成物中の固形分が３０重量％となるフォトスペーサー用樹脂組成物（１）を調製した。組成物の全固形分中におけるシリコーン含有量は１０．６重量％であった。
[Preparation of resin composition for photo spacer]
Resin solution for photo spacer (1) 16.3 g, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 7.5 g, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Propane-1-one (BASF, Irgacure907) 0.3 g, 2,4-diethylthioxatene-9-one (LAMBSON, Speedcure DETX) 0.1 g, and PGMAc 18.7 g were added to the composition. A resin composition (1) for a photospacer having a solid content of 30% by weight was prepared. The silicone content in the total solid content of the composition was 10.6% by weight.
実施例２
[フォトスペーサー用樹脂の合成]
片末端メタクリルシリコーン（信越化学工業株式会社製、ＫＦ―２０１２）８．９ｇ、グリシジルメタクリレート（ＧＭＡ）６ｇ、及び2,2'-アゾビス(2,4-ジメチルバレロニトリル)（ＡＤＶＮ）０．５ｇをプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＡｃ）１０７．１ｇに溶解させて窒素を吹き込みながら反応温度８０℃にて７時間反応させた。次にアクリル酸３．０ｇ、メトキノン０．１ｇ、及びトリエチルアンモニウムブロマイド０．１ｇを加え、空気を吹き込みながら反応温度９０℃で５３時間反応させた。５３時間後に酸価滴定を行い、アクリル酸由来のカルボン酸が消失していることを確認した。次に2-アクリロイルオキシエチルイソシアナート（昭和電工社製、カレンズＡＯＩ）４．５ｇを加え、空気を吹き込みながら反応温度６５℃で６時間反応させた。６時間後にＩＲ分析を行い、イソシアナート基の２２７０ｃｍ−１ピークが消失していることを確認した。最後にテトラヒドロ無水フタル酸を１．４ｇ加え、空気を吹き込みながら８０℃で４時間反応させて固形分濃度２２．２重量％の淡黄色透明のフォトスペーサー用樹脂溶液（２）を得た。４時間後ＩＲ分析を行い、酸無水物由来の１７８０ｃｍ−１ピークが消失していることを確認した。ＧＰＣにて分子量測定した結果、フォトスペーサー用樹脂のＭｗは２５，０００であり、フォトスペーサー用樹脂中のシリコーン含有量は３７．４重量％であった。
Example 2
[Synthesis of resin for photo spacer]
One-ended methacrylic silicone (manufactured by Shin-Etsu Chemical Co., Ltd., KF-2012) 8.9 g, glycidyl methacrylate (GMA) 6 g, and 2,2'-azobis (2,4-dimethylvaleronitrile) (ADVN) 0.5 g. It was dissolved in 107.1 g of propylene glycol monomethyl ether acetate (PGMAc) and reacted at a reaction temperature of 80 ° C. for 7 hours while blowing nitrogen. Next, 3.0 g of acrylic acid, 0.1 g of methquinone, and 0.1 g of triethylammonium bromide were added, and the reaction was carried out at a reaction temperature of 90 ° C. for 53 hours while blowing air. Acid value titration was performed 53 hours later, and it was confirmed that the carboxylic acid derived from acrylic acid had disappeared. Next, 4.5 g of 2-acryloyloxyethyl isocyanate (Kalens AOI manufactured by Showa Denko KK) was added, and the mixture was reacted at a reaction temperature of 65 ° C. for 6 hours while blowing air. After 6 hours, IR analysis was performed, and it was confirmed that the 2270 cm-1 peak of the isocyanate group had disappeared. Finally, 1.4 g of tetrahydrophthalic anhydride was added and reacted at 80 ° C. for 4 hours while blowing air to obtain a pale yellow transparent resin solution (2) for a photospacer having a solid content concentration of 22.2% by weight. After 4 hours, IR analysis was performed, and it was confirmed that the 1780 cm-1 peak derived from the acid anhydride had disappeared. As a result of measuring the molecular weight with GPC, the Mw of the photo spacer resin was 25,000, and the silicone content in the photo spacer resin was 37.4% by weight.
[フォトスペーサー用樹脂組成物の調製]
フォトスペーサー用樹脂溶液（２）２２．５ｇ、ジペンタエリスリトールヘキサアクリレート（日本化薬株式会社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）７．５ｇ、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オン（ＢＡＳＦ社製、Ｉｒｇａｃｕｒｅ９０７）０．３ｇ、２，４−ジエチルチオキサテン−９−オン（ＬＡＭＢＳＯＮ、Ｓｐｅｅｄｃｕｒｅ ＤＥＴＸ）０．１ｇ、及びＰＧＭＡｃ１２．５ｇを加え、組成物中の固形分が３０重量％となるフォトスペーサー用樹脂組成物（２）を調製した。組成物の全固形分中におけるシリコーン含有量は１４．５重量％であった。
[Preparation of resin composition for photo spacer]
Resin solution for photo spacer (2) 22.5 g, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 7.5 g, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Propane-1-one (BASF, Irgacure907) 0.3 g, 2,4-diethylthioxatene-9-one (LAMBSON, Speedcure DETX) 0.1 g, and PGMAc 12.5 g were added to the composition. A resin composition (2) for a photospacer having a solid content of 30% by weight was prepared. The silicone content in the total solid content of the composition was 14.5% by weight.
実施例３
[フォトスペーサー用樹脂の合成]
片末端メタクリルシリコーン（信越化学工業株式会社製、ＫＦ―２０１２）８．９ｇ、（２−メチル−２−エチル−１，３−ジオキソラン−４−イル）メチルアクリレート（大阪有機化学工業社製、ＭＥＤＯＬ−１０）５．２ｇ、グリシジルメタクリレート（ＧＭＡ）２１ｇ、及び2,2'-アゾビス(2,4-ジメチルバレロニトリル)（ＡＤＶＮ）０．９ｇを酢酸ブチル１１０ｇに溶解させて窒素を吹き込みながら反応温度６５℃にて７時間反応させた。次にアクリル酸１０．６ｇ、メトキノン０．１ｇ、及びトリエチルアンモニウムブロマイド０．１ｇを加え、空気を吹き込みながら反応温度９０℃で１３時間反応させた。１３時間後に酸価滴定を行い、アクリル酸由来のカルボン酸が消失していることを確認した。次に2-メタクリロイルオキシエチルイソシアナート（昭和電工社製、カレンズＭＯＩ）１７．２ｇを加え、空気を吹き込みながら反応温度６５℃で６時間反応させた。６時間後にＩＲ分析を行い、イソシアナート基の２２７０ｃｍ−１ピークが消失していることを確認した。最後に無水コハク酸を３．０ｇ加え、空気を吹き込みながら８０℃で４時間反応させて固形分濃度５９．９重量％の淡黄色透明のフォトスペーサー用樹脂溶液（３）を得た。４時間後ＩＲ分析を行い、酸無水物由来の１７８０ｃｍ−１ピークが消失していることを確認した。ＧＰＣにて分子量測定した結果、フォトスペーサー用樹脂のＭｗは３５，０００であり、フォトスペーサー用樹脂中のシリコーン含有量は１３．５重量％であった。
Example 3
[Synthesis of resin for photo spacer]
One-ended methacrylic silicone (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-2012) 8.9 g, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., MEDOL) -10) 5.2 g of 5.2 g, 21 g of glycidyl methacrylate (GMA), and 0.9 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (ADVN) are dissolved in 110 g of butyl acetate, and the reaction temperature is blown with nitrogen. The reaction was carried out at 65 ° C. for 7 hours. Next, 10.6 g of acrylic acid, 0.1 g of methquinone, and 0.1 g of triethylammonium bromide were added, and the mixture was reacted at a reaction temperature of 90 ° C. for 13 hours while blowing air. Acid value titration was performed 13 hours later, and it was confirmed that the carboxylic acid derived from acrylic acid had disappeared. Next, 17.2 g of 2-methacryloyloxyethyl isocyanate (Kalens MOI, manufactured by Showa Denko KK) was added, and the mixture was reacted at a reaction temperature of 65 ° C. for 6 hours while blowing air. After 6 hours, IR analysis was performed, and it was confirmed that the 2270 cm-1 peak of the isocyanate group had disappeared. Finally, 3.0 g of succinic anhydride was added and reacted at 80 ° C. for 4 hours while blowing air to obtain a pale yellow transparent resin solution (3) for a photospacer having a solid content concentration of 59.9% by weight. After 4 hours, IR analysis was performed, and it was confirmed that the 1780 cm-1 peak derived from the acid anhydride had disappeared. As a result of measuring the molecular weight with GPC, the Mw of the photo spacer resin was 35,000, and the silicone content in the photo spacer resin was 13.5% by weight.
[フォトスペーサー用樹脂組成物の調製]
フォトスペーサー用樹脂溶液（３）８．４ｇ、ジペンタエリスリトールヘキサアクリレート（日本化薬株式会社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）７．５ｇ、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オン（ＢＡＳＦ社製、Ｉｒｇａｃｕｒｅ９０７）０．３ｇ、２，４−ジエチルチオキサテン−９−オン（ＬＡＭＢＳＯＮ、Ｓｐｅｅｄｃｕｒｅ ＤＥＴＸ）０．１ｇ、及びＰＧＭＡｃ２６．６ｇを加え、組成物中の固形分が３０重量％となるフォトスペーサー用樹脂組成物（３）を調製した。組成物の全固形分中におけるシリコーン含有量は５．３重量％であった。
[Preparation of resin composition for photo spacer]
Resin solution for photo spacer (3) 8.4 g, dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 7.5 g, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Propane-1-one (BASF, Irgacure907) 0.3 g, 2,4-diethylthioxatene-9-one (LAMBSON, Speedcure DETX) 0.1 g, and PGMAc 26.6 g were added to the composition. A resin composition (3) for a photospacer having a solid content of 30% by weight was prepared. The silicone content in the total solid content of the composition was 5.3% by weight.
実施例４
[フォトスペーサー用樹脂の合成]
片末端メタクリルシリコーン（信越化学工業株式会社製、ＫＦ―２０１２）８．９ｇ、（２−メチル−２−エチル−１，３−ジオキソラン−４−イル）メチルアクリレート（大阪有機化学工業社製、ＭＥＤＯＬ−１０）５．２ｇ、グリシジルメタクリレート（ＧＭＡ）１０ｇ、及び2,2'-アゾビス(2,4-ジメチルバレロニトリル)（ＡＤＶＮ）０．６ｇを酢酸ブチル６５ｇに溶解させて窒素を吹き込みながら反応温度６５℃にて７時間反応させた。次にアクリル酸５．１ｇ、メトキノン０．１ｇ、及びトリエチルアンモニウムブロマイド０．１ｇを加え、空気を吹き込みながら反応温度９０℃で１５時間反応させた。１５時間後に酸価滴定を行い、アクリル酸由来のカルボン酸が消失していることを確認した。次に2-アクリロイルオキシエチルイソシアナート（昭和電工社製、カレンズＡＯＩ）７．４ｇを加え、空気を吹き込みながら反応温度６５℃で５時間反応させた。５時間後にＩＲ分析を行い、イソシアナート基の２２７０ｃｍ−１ピークが消失していることを確認した。最後に無水コハク酸を１．４ｇ加え、空気を吹き込みながら８０℃で４時間反応させて固形分濃度５８．５重量％の淡黄色透明のフォトスペーサー用樹脂溶液（４）を得た。４時間後ＩＲ分析を行い、酸無水物由来の１７８０ｃｍ−１ピークが消失していることを確認した。ＧＰＣにて分子量測定した結果、フォトスペーサー用樹脂のＭｗは３７，０００であり、フォトスペーサー用樹脂中のシリコーン含有量は２３．４重量％であった。
Example 4
[Synthesis of resin for photo spacer]
One-ended methacrylic silicone (manufactured by Shinetsu Chemical Industry Co., Ltd., KF-2012) 8.9 g, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., MEDOL) -10) 5.2 g of 5.2 g, 10 g of glycidyl methacrylate (GMA), and 0.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (ADVN) are dissolved in 65 g of butyl acetate, and the reaction temperature is blown with nitrogen. The reaction was carried out at 65 ° C. for 7 hours. Next, 5.1 g of acrylic acid, 0.1 g of methquinone, and 0.1 g of triethylammonium bromide were added, and the mixture was reacted at a reaction temperature of 90 ° C. for 15 hours while blowing air. Acid value titration was performed after 15 hours, and it was confirmed that the carboxylic acid derived from acrylic acid had disappeared. Next, 7.4 g of 2-acryloyloxyethyl isocyanate (Kalens AOI manufactured by Showa Denko KK) was added, and the mixture was reacted at a reaction temperature of 65 ° C. for 5 hours while blowing air. IR analysis was performed 5 hours later, and it was confirmed that the 2270 cm-1 peak of the isocyanate group had disappeared. Finally, 1.4 g of succinic anhydride was added and reacted at 80 ° C. for 4 hours while blowing air to obtain a pale yellow transparent resin solution (4) for a photospacer having a solid content concentration of 58.5% by weight. After 4 hours, IR analysis was performed, and it was confirmed that the 1780 cm-1 peak derived from the acid anhydride had disappeared. As a result of measuring the molecular weight with GPC, the Mw of the photo spacer resin was 37,000, and the silicone content in the photo spacer resin was 23.4% by weight.
[フォトスペーサー用樹脂組成物の調製]
フォトスペーサー用樹脂溶液（４）８．６ｇ、ジペンタエリスリトールヘキサアクリレート（日本化薬株式会社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）７．５ｇ、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オン（ＢＡＳＦ社製、Ｉｒｇａｃｕｒｅ９０７）０．３ｇ、２，４−ジエチルチオキサテン−９−オン（ＬＡＭＢＳＯＮ、Ｓｐｅｅｄｃｕｒｅ ＤＥＴＸ）０．１ｇ、及びＰＧＭＡｃ２６．４ｇを加え、組成物中の固形分が３０重量％となるフォトスペーサー用樹脂組成物（４）を調製した。組成物の全固形分中におけるシリコーン含有量は９．１重量％であった。
[Preparation of resin composition for photo spacer]
Resin solution for photo spacer (4) 8.6 g, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 7.5 g, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Propane-1-one (BASF, Irgacure907) 0.3 g, 2,4-diethylthioxatene-9-one (LAMBSON, Speedcure DETX) 0.1 g, and PGMAc 26.4 g were added to the composition. A resin composition (4) for a photospacer having a solid content of 30% by weight was prepared. The silicone content in the total solid content of the composition was 9.1% by weight.
比較例１
[フォトスペーサー用樹脂の合成]
グリシジルメタクリレート（ＧＭＡ）２０ｇ、及び2,2'-アゾビス(2,4-ジメチルバレロニトリル)（ＡＤＶＮ）０．６ｇをプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＡｃ）８２ｇに溶解させて窒素を吹き込みながら反応温度６５℃にて７時間反応させた。次にアクリル酸１０．１ｇ、メトキノン０．１ｇ、及びトリエチルアンモニウムブロマイド０．１ｇを加え、空気を吹き込みながら反応温度９０℃で１４時間反応させた。１４時間後に酸価滴定を行い、アクリル酸由来のカルボン酸が消失していることを確認した。次に2-アクリロイルオキシエチルイソシアナート（昭和電工社製、カレンズＡＯＩ）１４．９ｇを加え、空気を吹き込みながら反応温度６５℃で６時間反応させた。６時間後にＩＲ分析を行い、イソシアナート基の２２７０ｃｍ−１ピークが消失していることを確認した。最後に無水コハク酸を２．８ｇ加え、空気を吹き込みながら８０℃で４時間反応させて固形分濃度５８．３重量％の淡黄色透明のフォトスペーサー用樹脂溶液（５）を得た。４時間後ＩＲ分析を行い、酸無水物由来の１７８０ｃｍ−１ピークが消失していることを確認した。ＧＰＣにて分子量測定した結果、フォトスペーサー用樹脂のＭｗは３５，０００であり、フォトスペーサー用樹脂中のシリコーン含有量は０重量％であった。
Comparative Example 1
[Synthesis of resin for photo spacer]
20 g of glycidyl methacrylate (GMA) and 0.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (ADVN) are dissolved in 82 g of propylene glycol monomethyl ether acetate (PGMAc), and the reaction temperature is 65 while blowing nitrogen. The reaction was carried out at ° C. for 7 hours. Next, 10.1 g of acrylic acid, 0.1 g of methquinone, and 0.1 g of triethylammonium bromide were added, and the mixture was reacted at a reaction temperature of 90 ° C. for 14 hours while blowing air. Acid value titration was performed 14 hours later, and it was confirmed that the carboxylic acid derived from acrylic acid had disappeared. Next, 14.9 g of 2-acryloyloxyethyl isocyanate (Kalens AOI manufactured by Showa Denko KK) was added, and the mixture was reacted at a reaction temperature of 65 ° C. for 6 hours while blowing air. After 6 hours, IR analysis was performed, and it was confirmed that the 2270 cm-1 peak of the isocyanate group had disappeared. Finally, 2.8 g of succinic anhydride was added and reacted at 80 ° C. for 4 hours while blowing air to obtain a pale yellow transparent resin solution (5) for a photospacer having a solid content concentration of 58.3% by weight. After 4 hours, IR analysis was performed, and it was confirmed that the 1780 cm-1 peak derived from the acid anhydride had disappeared. As a result of measuring the molecular weight with GPC, the Mw of the photo spacer resin was 35,000, and the silicone content in the photo spacer resin was 0% by weight.
[フォトスペーサー用樹脂組成物の調製]
フォトスペーサー用樹脂溶液（５）８．６ｇ、ジペンタエリスリトールヘキサアクリレート（日本化薬株式会社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）６．５ｇ、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オン（ＢＡＳＦ社製、Ｉｒｇａｃｕｒｅ９０７）０．３ｇ、２，４−ジエチルチオキサテン−９−オン（ＬＡＭＢＳＯＮ、Ｓｐｅｅｄｃｕｒｅ ＤＥＴＸ）０．１ｇ、及びＰＧＭＡｃ２４．１ｇを加え、組成物中の固形分が３０重量％となるフォトスペーサー用樹脂組成物（５）を調製した。組成物の全固形分中におけるシリコーン含有量は０重量％であった。
[Preparation of resin composition for photo spacer]
Resin solution for photo spacer (5) 8.6 g, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 6.5 g, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Propane-1-one (BASF, Irgacure907) 0.3 g, 2,4-diethylthioxatene-9-one (LAMBSON, Speedcure DETX) 0.1 g, and PGMAc24.1 g were added to the composition. A resin composition (5) for a photospacer having a solid content of 30% by weight was prepared. The silicone content in the total solid content of the composition was 0% by weight.
比較例２
[フォトスペーサー用樹脂組成物の調製]
フォトスペーサー用樹脂溶液（５）８．６ｇ、ジペンタエリスリトールヘキサアクリレート（日本化薬株式会社製、ＫＡＹＡＲＡＤ ＤＰＨＡ）４ｇ、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オン（ＢＡＳＦ社製、Ｉｒｇａｃｕｒｅ９０７）０．３ｇ、２，４−ジエチルチオキサテン−９−オン（ＬＡＭＢＳＯＮ、Ｓｐｅｅｄｃｕｒｅ ＤＥＴＸ）０．１ｇ、及びＰＧＭＡｃ１８．２ｇを加え、組成物中の固形分が３０重量％となるフォトスペーサー用樹脂組成物（６）を調製した。組成物の全固形分中におけるシリコーン含有量は０重量％であった。
Comparative Example 2
[Preparation of resin composition for photo spacer]
Resin solution for photo spacer (5) 8.6 g, dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 4 g, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane Add 0.3 g of -1-one (BASF, Irgacure907), 0.1 g of 2,4-diethylthioxatin-9-one (LAMBSON, Speedcure DETX), and 18.2 g of PGMAc, and the solid content in the composition. A resin composition (6) for a photospacer having a content of 30% by weight was prepared. The silicone content in the total solid content of the composition was 0% by weight.
[フォトスペーサーの形成]
１０ｃｍ×１０ｃｍ四方の各ガラス基板上に、スピンコーターを用いて実施例１〜４、比較例１及び２で調製したフォトスペーサー用樹脂組成物（１）〜（６）をそれぞれ塗布して塗膜を形成し、当該塗膜を９０℃のホットプレート上で２分間加熱して溶剤を完全に除去した。その後、得られた塗膜に対して、１ｃｍ２あたり１００個、直径８、９、１０、又は１１μｍの異なる径の開口部を有する複数のフォトスペーサー形成用マスクを通して、超高圧水銀灯の光を１００ｍＪ／ｃｍ２照射した（ｉ線換算で照度２０ｍＷ／ｃｍ２）。なお、マスクと基板との間隔（露光ギャップ）１００μｍにて露光を行った。その後、０．０５％ＫＯＨ水溶液を用いてアルカリ現像を行った。水洗したのち、２３０℃で３０分間ポストベークを行い、フォトスペーサーを形成した。なお、マスク開口径を調整することにより所望のフォトスペーサーを形成することができる。フォトスペーサーは、高さ３μｍに揃え、フォトスペーサーの下底径が９〜１１μｍ、上底径が６〜７μｍである円柱状のフォトスペーサーを選択して下記の測定を行った。
[Formation of photo spacer]
The resin compositions (1) to (6) for photospacers prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were applied to each glass substrate of 10 cm × 10 cm square using a spin coater to obtain a coating film. Was formed, and the coating film was heated on a hot plate at 90 ° C. for 2 minutes to completely remove the solvent. Then, 100 mJ of light from an ultra-high pressure mercury lamp was applied to the obtained coating film through a plurality of photo spacer forming masks having openings having different diameters of 8, 9, 10, or 11 μm per cm 2. / cm 2 was irradiated (irradiance 20 mW / cm 2 in terms of i-line). The exposure was performed at a distance (exposure gap) of 100 μm between the mask and the substrate. Then, alkali development was carried out using a 0.05% KOH aqueous solution. After washing with water, post-baking was performed at 230 ° C. for 30 minutes to form a photo spacer. A desired photo spacer can be formed by adjusting the mask opening diameter. The photo spacers had a height of 3 μm, and a columnar photo spacer having a lower base diameter of 9 to 11 μm and an upper base diameter of 6 to 7 μm was selected and the following measurements were performed.
〔測定方法〕
（変形量及び復元率の測定）
上記で形成した実施例１〜４、比較例１及び２のフォトスペーサー（高さ３μｍ）に、微小硬さ試験機（フィッシャーインストルメンツ社製、ＦＩＳＣＨＥＲＳＣＯＰＥ ＨＭ−２０００）を用いて、直径５０μｍの平面圧子により、負荷速度および除荷速度をともに２.０ｍＮ／秒として、２０ｍＮまで荷重を負荷したのち、５秒間保持し、その後０ｍＮまで除荷した後、５秒間保持し、負荷時の荷重−変形量曲線、及び除荷時の荷重−変形量曲線を作成した。そして、負荷時の荷重２０ｍＮでの変形量をＬ１、除荷時の荷重０ｍＮでの変形量をＬ２として、下記式により、変形量と復元率を算出した。
変形量（μｍ）＝Ｌ１
復元率（％）＝（Ｌ１−Ｌ２）×１００／Ｌ１
〔Measuring method〕
(Measurement of deformation amount and restoration rate)
A flat surface having a diameter of 50 μm was used on the photospacers (height 3 μm) of Examples 1 to 4 and Comparative Examples 1 and 2 formed above using a microhardness tester (FISCHERSCOPE HM-2000 manufactured by Fisher Instruments). With an indenter, the load speed and unloading speed are both set to 2.0 mN / sec, and after loading to 20 mN, the load is held for 5 seconds, then unloading to 0 mN, and then held for 5 seconds. An isoquantity curve and a load-deformation amount curve at the time of unloading were created. Then, the deformation amount and the restoration rate were calculated by the following formulas, where the deformation amount at a load of 20 mN under load was L1 and the deformation amount at a load of 0 mN at the time of unloading was L2.
Deformation amount (μm) = L1
Restoration rate (%) = (L1-L2) x 100 / L1
表１の結果から、実施例１〜４のフォトスペーサーは、高柔軟性と高復元性とを両立していることがわかる。また、実施例３及び４では、実施例１及び２に比べて、フォトスペーサー用樹脂の合成時間が大幅に短縮されていることがわかる。比較例１のフォトスペーサーは、復元率は高いが、変形量が小さい（硬い）ことがわかる。比較例２のフォトスペーサーは、変形量は大きい（柔らかい）が、復元率が低いことがわかる。 From the results in Table 1, it can be seen that the photospacers of Examples 1 to 4 have both high flexibility and high resilience. Further, it can be seen that in Examples 3 and 4, the synthesis time of the photo spacer resin is significantly shortened as compared with Examples 1 and 2. It can be seen that the photo spacer of Comparative Example 1 has a high restoration rate but a small amount of deformation (hard). It can be seen that the photo spacer of Comparative Example 2 has a large amount of deformation (soft) but a low restoration rate.
本発明のフォトスペーサー及びカラーフィルタは、液晶表示装置の構成部材として好適に用いられる。
The photo spacer and color filter of the present invention are suitably used as constituent members of a liquid crystal display device.
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