KR20230014841A - Copolymer and photosensitive resin composition for color filter - Google Patents
Copolymer and photosensitive resin composition for color filter Download PDFInfo
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- KR20230014841A KR20230014841A KR1020237001060A KR20237001060A KR20230014841A KR 20230014841 A KR20230014841 A KR 20230014841A KR 1020237001060 A KR1020237001060 A KR 1020237001060A KR 20237001060 A KR20237001060 A KR 20237001060A KR 20230014841 A KR20230014841 A KR 20230014841A
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- South Korea
- Prior art keywords
- structural unit
- meth
- acrylate
- copolymer
- derived
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 133
- 239000011342 resin composition Substances 0.000 title claims abstract description 88
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims abstract description 86
- 239000002904 solvent Substances 0.000 claims abstract description 84
- 239000002253 acid Substances 0.000 claims abstract description 38
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 34
- 239000003085 diluting agent Substances 0.000 claims abstract description 32
- 239000003086 colorant Substances 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 167
- -1 Methylpropylideneamino Chemical group 0.000 claims description 94
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 36
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 30
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 24
- 239000000049 pigment Substances 0.000 claims description 22
- 239000003513 alkali Substances 0.000 claims description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 17
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- 150000004702 methyl esters Chemical class 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000004112 carboxyamino group Chemical group [H]OC(=O)N([H])[*] 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004494 ethyl ester group Chemical group 0.000 claims description 6
- FPELGIYDSAIJQP-UHFFFAOYSA-N CC(C(O)=O)=CCCNC(N1N=C(C)C=C1C)=O Chemical compound CC(C(O)=O)=CCCNC(N1N=C(C)C=C1C)=O FPELGIYDSAIJQP-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 description 42
- 229920000642 polymer Polymers 0.000 description 32
- 239000000203 mixture Substances 0.000 description 30
- 238000010494 dissociation reaction Methods 0.000 description 26
- 230000005593 dissociations Effects 0.000 description 26
- 238000000576 coating method Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 238000003860 storage Methods 0.000 description 17
- 238000004040 coloring Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 239000002270 dispersing agent Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
- 238000011161 development Methods 0.000 description 10
- 230000018109 developmental process Effects 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 8
- 239000002981 blocking agent Substances 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000012948 isocyanate Substances 0.000 description 8
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 5
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 5
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 5
- WLTSXAIICPDFKI-UHFFFAOYSA-N 3-dodecene Chemical compound CCCCCCCCC=CCC WLTSXAIICPDFKI-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 4
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 229960001047 methyl salicylate Drugs 0.000 description 4
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000980 acid dye Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000001056 green pigment Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- 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 2
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- 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 2
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-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
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- BEQIIZJSZSVJJK-UHFFFAOYSA-M chembl2028372 Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1N=NC1=C(O)C=CC2=CC=CC=C12 BEQIIZJSZSVJJK-UHFFFAOYSA-M 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- 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
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Abstract
블록 이소시아나토기를 갖는 구성 단위 (a) 와 산기를 갖는 구성 단위 (b) 와 에폭시기를 갖는 구성 단위 (c) 를 함유하는 공중합체 (A), 용제 (B), 반응성 희석제 (C), 광 중합 개시제 (D) 및 착색제 (E) 를 함유하는 컬러 필터용 감광성 수지 조성물.A copolymer (A) containing a structural unit (a) having a block isocyanato group, a structural unit (b) having an acid group, and a structural unit (c) having an epoxy group, a solvent (B), a reactive diluent (C), The photosensitive resin composition for color filters containing a photoinitiator (D) and a coloring agent (E).
Description
본 발명은, 신규 공중합체, 그것을 함유하는 컬러 필터용 감광성 수지 조성물, 컬러 필터, 그것을 구비하는 화상 표시 소자 및 컬러 필터의 제조 방법에 관한 것이다.The present invention relates to a novel copolymer, a photosensitive resin composition for color filters containing the same, a color filter, an image display element including the same, and a method for producing the color filter.
최근, 자원 절약이나 에너지 절약의 관점에서, 각종 코팅, 인쇄, 도료, 접착제 등의 분야에 있어서, 자외선이나 전자선 등의 활성 에너지선에 의해 경화 가능한 감광성 수지 조성물이 널리 사용되고 있다. 또, 프린트 배선 기판 등의 전자 재료의 분야에 있어서도, 활성 에너지선에 의해 경화 가능한 감광성 수지 조성물이, 솔더 레지스트나 컬러 필터용 레지스트 등에 사용되고 있다. 또한, 경화 가능한 감광성 수지 조성물에 대한 요구 특성은, 점점 더 다양하게 또한 고도로 되고 있는데, 그 중에서도, 생산성을 고려한 단시간 경화성, 적용하는 부재의 열적 데미지를 억제하는 저온 경화성이 요구되고 있다.In recent years, from the viewpoint of resource saving and energy saving, photosensitive resin compositions curable by active energy rays such as ultraviolet rays and electron beams have been widely used in fields such as various coatings, printing, paints, and adhesives. Moreover, also in the field of electronic materials, such as a printed wiring board, the photosensitive resin composition hardenable by an active energy ray is used for a solder resist, a resist for color filters, etc. In addition, the required properties of the curable photosensitive resin composition are becoming increasingly diverse and highly advanced, and among them, short-time curability considering productivity and low-temperature curability that suppresses thermal damage to members to be applied are required.
컬러 필터는, 일반적으로, 유리 기판 등의 투명 기판과, 투명 기판 상에 형성된 적 (R), 녹 (G) 및 청 (B) 의 화소와, 화소의 경계에 형성되는 블랙 매트릭스와, 화소 및 블랙 매트릭스 상에 형성되는 보호막으로 구성된다. 이와 같은 구성을 갖는 컬러 필터는, 통상, 투명 기판 상에 블랙 매트릭스, 화소 및 보호막을 순차 형성함으로써 제조된다. 화소 및 블랙 매트릭스 (이하, 화소 및 블랙 매트릭스를 「착색 패턴」이라고 한다.) 의 형성 방법으로는, 여러 가지 방법이 제안되어 있다. 그 중에서, 감광성 수지 조성물을 레지스트로서 사용하고, 도포, 노광, 현상 및 베이킹을 반복하는 포토리소그래피 공법으로 제작되는 안료/염료 분산법은, 내구성이 우수하고, 핀홀 등의 결함이 적은 착색 패턴을 부여하기 때문에, 현재의 주류가 되고 있다.A color filter generally includes a transparent substrate such as a glass substrate, red (R), green (G), and blue (B) pixels formed on the transparent substrate, a black matrix formed on the boundary between the pixels, and pixels and It is composed of a protective film formed on the black matrix. A color filter having such a structure is usually manufactured by sequentially forming a black matrix, pixels, and a protective film on a transparent substrate. As a method of forming the pixels and the black matrix (hereinafter, the pixels and the black matrix are referred to as "coloring patterns"), various methods have been proposed. Among them, a pigment/dye dispersion method produced by a photolithography method using a photosensitive resin composition as a resist and repeating application, exposure, development, and baking provides a coloring pattern with excellent durability and fewer defects such as pinholes. Because of that, it has become the current mainstream.
일반적으로, 포토리소그래피 공법에 사용되는 감광성 수지 조성물은, 알칼리 가용성 수지, 반응성 희석제, 광 중합 개시제, 착색제 및 용제를 함유한다. 안료/염료 분산법에서는, 상기의 이점을 가지고 있는 반면, 블랙 매트릭스, R, G, B 의 패턴을 반복 형성하는 점에서, 높은 내열성이 요구되고, 높은 베이킹 온도에 견딜 수 있는 착색제로서 사용할 수 있는 착색제의 종류가 한정되는 등의 제한이 있는 것이, 자주 문제가 된다.In general, the photosensitive resin composition used in the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant and a solvent. In the pigment/dye dispersion method, while having the above advantages, high heat resistance is required in terms of repeating black matrix, R, G, and B patterns, and it can be used as a colorant that can withstand high baking temperatures. It is often a problem that there are restrictions such as the type of colorant being limited.
특허문헌 1 은, 알칼리 가용성 수지, 에틸렌성 불포화 결합을 갖는 중합성 화합물, 감방사선성 중합 개시제, 착색제 및 3-아미노벤젠술폰산에틸 등의 화합물을 사용함으로써, 저온 경화가 가능하고 보존 안정성을 향상시킨 착색 조성물을 개시하고 있다.Patent Document 1 is an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a radiation-sensitive polymerization initiator, a colorant, and a compound such as ethyl 3-aminobenzenesulfonate, which enables low-temperature curing and improves storage stability. A coloring composition is disclosed.
특허문헌 2 는, 염기성 물질에 의해 또는 염기성 물질의 존재하에서의 가열에 의해 최종 생성물로의 반응이 촉진되는 고분자 전구체와, 전자파의 조사 및 가열에 의해 염기를 발생하는 특정한 염기 발생제를 포함하는 감광성 수지 조성물을 사용함으로써 저온 경화를 가능하게 하고 있다.Patent Document 2 is a photosensitive resin containing a polymer precursor whose reaction to a final product is accelerated by heating with a basic substance or in the presence of a basic substance, and a specific base generator that generates a base by irradiation with electromagnetic waves and heating. Low-temperature hardening is made possible by using a composition.
최근에는, 전자 페이퍼 등의 플렉시블 디스플레이가 보급되고 있다. 이 플렉시블 디스플레이의 기판으로는, 폴리에틸렌테레프탈레이트 등의 플라스틱 기판이 검토되고 있다. 이 기판은 베이킹시에 신장 또는 수축하는 성질이 있어, 베이킹 공정의 저온화가 필요시되고 있다. 그러나, 특허문헌 1 에서 달성되는 레벨로는, 상기의 요구를 만족시키기에는 불충분하다. 또, 특허문헌 2 에서는, 저온 경화성을 향상시킨 반면, 보존 안정성이 낮고, 실용화는 곤란하다.In recent years, flexible displays such as electronic paper have spread. As a substrate of this flexible display, plastic substrates such as polyethylene terephthalate are being studied. Since this substrate has a property of elongating or contracting during baking, it is necessary to lower the temperature of the baking process. However, the level achieved in Patent Literature 1 is insufficient to satisfy the above requirements. Further, in Patent Literature 2, low-temperature curability is improved, but storage stability is low, and practical use is difficult.
본 발명은, 상기의 과제를 해결하기 위해 이루어진 것으로, 현상성 및 보존 안정성이 양호함과 함께, 저온에서 경화시켜도 내용제성이 우수한 착색 패턴을 부여하는 컬러 필터용 감광성 수지 조성물, 및 그 감광성 수지 조성물의 조제에 유용한 공중합체를 제공하는 것을 목적으로 한다.The present invention has been made to solve the above problems, and while having good developability and storage stability, a photosensitive resin composition for color filters that imparts a colored pattern having excellent solvent resistance even when cured at low temperatures, and the photosensitive resin composition thereof Its object is to provide a copolymer useful for the preparation of
또, 본 발명은, 내용제성이 우수한 착색 패턴을 갖는 컬러 필터 및 그 제조 방법 그리고 그 컬러 필터를 구비하는 화상 표시 소자를 제공하는 것을 목적으로 한다.Moreover, an object of this invention is to provide the color filter which has a coloring pattern excellent in solvent resistance, its manufacturing method, and the image display element provided with the color filter.
즉, 본 발명은, 이하의 [1] ∼ [25] 로 나타낸다.That is, this invention is represented by the following [1] - [25].
[1] 블록 이소시아나토기를 갖는 구성 단위 (a), 산기를 갖는 구성 단위 (b) 및 에폭시기를 갖는 구성 단위 (c) 를 함유하는 것을 특징으로 하는 공중합체 (A).[1] A copolymer (A) characterized by containing a structural unit (a) having a block isocyanato group, a structural unit (b) having an acid group, and a structural unit (c) having an epoxy group.
[2] 상기 블록 이소시아나토기를 갖는 구성 단위 (a) 가, 블록 이소시아나토기 함유 (메트)아크릴레이트 유래의 구성 단위이고, 상기 블록 이소시아나토기 함유 (메트)아크릴레이트의 블록 이소시아나토기의 해리율이 100 ℃ 에서 30 분 가열했을 때, 5 ∼ 99 질량% 인 [1] 에 기재된 공중합체.[2] The structural unit (a) having a block isocyanato group is a structural unit derived from a (meth)acrylate containing a block isocyanato group, and the block isocyanato group-containing (meth)acrylate The copolymer according to [1], wherein the cyanato group dissociation rate is 5 to 99% by mass when heated at 100°C for 30 minutes.
[3] 상기 블록 이소시아나토기를 갖는 구성 단위 (a) 의 블록제가, 말론산디에틸, 3,5-디메틸피라졸, 메틸에틸케토옥심, 2-하이드록시벤조산메틸, 4-하이드록시벤조산메틸 및 3,5-자일레놀로 이루어지는 군에서 선택되는 1 종 이상인 [1] 또는 [2] 에 기재된 공중합체.[3] The blocking agent for the structural unit (a) having a block isocyanato group is diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate and 3,5-xylenol, and the copolymer according to [1] or [2], which is at least one selected from the group consisting of.
[4] 상기 산기를 갖는 구성 단위 (b) 가, 불포화 카르복실산 유래의 구성 단위인 [1] ∼ [3] 중 어느 하나에 기재된 공중합체.[4] The copolymer according to any one of [1] to [3], wherein the structural unit (b) having an acid group is a structural unit derived from an unsaturated carboxylic acid.
[5] 상기 에폭시기를 갖는 구성 단위 (c) 가, 에폭시기 함유 (메트)아크릴레이트 유래의 구성 단위인 [1] ∼ [4] 중 어느 하나에 기재된 공중합체.[5] The copolymer according to any one of [1] to [4], wherein the structural unit (c) having an epoxy group is a structural unit derived from an epoxy group-containing (meth)acrylate.
[6] 상기 공중합체 (A) 가, 상기 블록 이소시아나토기를 갖는 구성 단위 (a) 를 1 ∼ 60 몰%, 상기 산기를 갖는 구성 단위 (b) 를 5 ∼ 65 몰% 및 상기 에폭시기를 갖는 구성 단위 (c) 를 5 ∼ 65 몰% 함유하는 [1] ∼ [5] 중 어느 하나에 기재된 공중합체.[6] The copolymer (A) contains 1 to 60 mol% of the structural unit (a) having the block isocyanato group, 5 to 65 mol% of the structural unit (b) having the acid group, and the epoxy group The copolymer according to any one of [1] to [5], containing 5 to 65 mol% of the structural unit (c).
[7] 상기 공중합체 (A) 에 있어서의 상기 블록 이소시아나토기를 갖는 구성 단위 (a) 와 상기 에폭시를 갖는 구성 단위 (c) 의 몰비율이, 10 : 90 ∼ 75 : 25 인 [1] ∼ [6] 중 어느 하나에 기재된 공중합체.[7] The molar ratio of the structural unit (a) having the block isocyanato group in the copolymer (A) and the structural unit (c) having the epoxy is 10: 90 to 75: 25 [1 ] to the copolymer described in any one of [6].
[8] 상기 공중합체 (A) 가, 메타크릴산2-(3,5-디메틸피라졸-1-일)카르보닐아미노에틸, 메타크릴산2-[O-(1'-메틸프로필리덴아미노)카르복시아미노]에틸, 말론산-2-[[[2-메틸-1-옥소-2-프로페닐]옥시]에틸]아미노]카르보닐]-1,3디에틸에스테르, 벤조산-4-[[[[2-[(2-메틸-1-옥소-2-프로펜-1-일)옥시]에틸]아민]카르보닐]옥시]메틸에스테르, 벤조산-2-[[[[2-[(2-메틸-1-옥시-2-프로펜-1-일)옥시]에틸]아민]카르보닐]옥시]메틸에스테르 및 2-프로펜산-2-메틸-2-[[(3,5-디메틸페녹시)카르보닐]아민]에틸에스테르로 이루어지는 군에서 선택되는 적어도 1 종 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜(메트)아크릴레이트 유래의 구성 단위 (c) 와, 디시클로펜타닐(메트)아크릴레이트 및 메틸(메트)아크릴레이트로 이루어지는 군에서 선택되는 적어도 1 종 유래의 구성 단위 (e) 를 함유하는 [1] ∼ [7] 중 어느 하나에 기재된 공중합체.[8] The copolymer (A) is methacrylic acid 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl, methacrylic acid 2-[O-(1'-methylpropylideneamino )Carboxyamino]ethyl, malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, benzoic acid-4-[[ [[2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2 -methyl-1-oxy-2-propen-1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester and 2-propenoic acid-2-methyl-2-[[(3,5-dimethylphenone xi) carbonyl] amine] ethyl ester derived from at least one structural unit (a), (meth)acrylic acid-derived structural unit (b), and glycidyl (meth)acrylate-derived Any one of [1] to [7] containing a structural unit (c) and a structural unit (e) derived from at least one selected from the group consisting of dicyclopentanyl (meth)acrylate and methyl (meth)acrylate; The copolymer described in one.
[9] 상기 공중합체 (A) 가, 수산기를 갖는 구성 단위 (d) 를 추가로 함유하는 [1] ∼ [8] 중 어느 하나에 기재된 공중합체.[9] The copolymer according to any one of [1] to [8], wherein the copolymer (A) further contains a structural unit (d) having a hydroxyl group.
[10] 상기 공중합체 (A) 가, 메타크릴산2-(3,5-디메틸피라졸-1-일)카르보닐아미노에틸, 메타크릴산2-[O-(1'-메틸프로필리덴아미노)카르복시아미노]에틸, 말론산-2-[[[2-메틸-1-옥소-2-프로페닐]옥시]에틸]아미노]카르보닐]-1,3디에틸에스테르, 벤조산-4-[[[[2-[(2-메틸-1-옥소-2-프로펜-1-일)옥시]에틸]아민]카르보닐]옥시]메틸에스테르, 벤조산-2-[[[[2-[(2-메틸-1-옥시-2-프로펜-1-일)옥시]에틸]아민]카르보닐]옥시]메틸에스테르 및 2-프로펜산-2-메틸-2-[[(3,5-디메틸페녹시)카르보닐]아민]에틸에스테르로 이루어지는 군에서 선택되는 적어도 1 종 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜(메트)아크릴레이트 유래의 구성 단위 (c) 와, 2-하이드록시에틸메타크릴레이트 유래의 구성 단위 (d) 와, 디시클로펜타닐(메트)아크릴레이트 및 메틸(메트)아크릴레이트로 이루어지는 군에서 선택되는 적어도 1 종 유래의 구성 단위 (e) 를 함유하는 [9] 에 기재된 공중합체.[10] The copolymer (A) is methacrylic acid 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl, methacrylic acid 2-[O-(1'-methylpropylideneamino )Carboxyamino]ethyl, malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, benzoic acid-4-[[ [[2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2 -methyl-1-oxy-2-propen-1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester and 2-propenoic acid-2-methyl-2-[[(3,5-dimethylphenone xi) carbonyl] amine] ethyl ester derived from at least one structural unit (a), (meth)acrylic acid-derived structural unit (b), and glycidyl (meth)acrylate-derived Structural unit (c), structural unit (d) derived from 2-hydroxyethyl methacrylate, and derived from at least one member selected from the group consisting of dicyclopentanyl (meth)acrylate and methyl (meth)acrylate The copolymer as described in [9] containing the structural unit (e).
[11] 상기 공중합체 (A) 가, 메타크릴산2-[O-(1'-메틸프로필리덴아미노)카르복시아미노]에틸 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜(메트)아크릴레이트 유래의 구성 단위 (c) 와, 디시클로펜타닐(메트)아크릴레이트 유래의 구성 단위 (e) 를 함유하는 [8] 에 기재된 공중합체.[11] The copolymer (A) is composed of a structural unit (a) derived from 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylic acid and a structural unit derived from (meth)acrylic acid ( The copolymer according to [8], comprising b), a structural unit (c) derived from glycidyl (meth)acrylate, and a structural unit (e) derived from dicyclopentanyl (meth)acrylate.
[12] 상기 공중합체 (A) 가, 메타크릴산2-(3,5-디메틸피라졸-1-일)카르보닐아미노에틸 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜(메트)아크릴레이트 유래의 구성 단위 (c) 와, 디시클로펜타닐(메트)아크릴레이트 유래의 구성 단위 (e) 를 함유하는 [8] 에 기재된 공중합체.[12] The copolymer (A) is composed of a structural unit (a) derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylic acid and a structural unit derived from (meth)acrylic acid The copolymer according to [8], comprising (b), a structural unit (c) derived from glycidyl (meth)acrylate, and a structural unit (e) derived from dicyclopentanyl (meth)acrylate.
[13] 상기 공중합체 (A) 가, 메타크릴산2-(3,5-디메틸피라졸-1-일)카르보닐아미노에틸 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜(메트)아크릴레이트 유래의 구성 단위 (c) 와, 2-하이드록시에틸메타크릴레이트 유래의 구성 단위 (d) 와, 디시클로펜타닐(메트)아크릴레이트 유래의 구성 단위 (e) 를 함유하는 [10] 에 기재된 공중합체.[13] The copolymer (A) contains a structural unit (a) derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylic acid and a structural unit derived from (meth)acrylic acid (b), a structural unit derived from glycidyl (meth)acrylate (c), a structural unit derived from 2-hydroxyethyl methacrylate (d), and a structural unit derived from dicyclopentanyl (meth)acrylate The copolymer according to [10], containing the unit (e).
[14] 상기 공중합체 (A) 가, 말론산-2-[[[2-메틸-1-옥소-2-프로페닐]옥시]에틸]아미노]카르보닐]-1,3디에틸에스테르 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜(메트)아크릴레이트 유래의 구성 단위 (c) 와, 디시클로펜타닐(메트)아크릴레이트 유래의 구성 단위 (e) 를 함유하는 [8] 에 기재된 공중합체.[14] The copolymer (A) is derived from malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester Structural unit (a), structural unit (b) derived from (meth)acrylic acid, structural unit (c) derived from glycidyl (meth)acrylate, and structural unit derived from dicyclopentanyl (meth)acrylate ( The copolymer described in [8] containing e).
[15] 상기 공중합체 (A) 가, 수산기를 갖는 구성 단위 (d) 및 상기 구성 단위 (a) ∼ (d) 이외의 구성 단위 (e) 를 추가로 함유하고, [15] The copolymer (A) further contains a structural unit (d) having a hydroxyl group and a structural unit (e) other than the structural units (a) to (d),
상기 공중합체 (A) 가, 상기 블록 이소시아나토기를 갖는 구성 단위 (a) 를 1 ∼ 40 몰%, 상기 산기를 갖는 구성 단위 (b) 를 1 ∼ 60 몰%, 상기 에폭시기를 갖는 구성 단위 (c) 를 1 ∼ 70 몰%, 상기 수산기를 갖는 구성 단위 (d) 를 0 몰% 초과 ∼ 50 몰% 및 상기 구성 단위 (e) 를 0 몰% 초과 ∼ 80 몰% 함유하는 [1] ∼ [5] 중 어느 하나에 기재된 공중합체.The copolymer (A) contains 1 to 40 mol% of the structural unit (a) having the block isocyanato group, 1 to 60 mol% of the structural unit (b) having the acid group, and the structural unit having the epoxy group [1] containing 1 to 70 mol% of (c), more than 0 mol% to 50 mol% of the structural unit (d) having the hydroxyl group, and more than 0 mol% to 80 mol% of the structural unit (e) The copolymer described in any one of [5].
[16] 상기 공중합체 (A) 가, 수산기를 갖는 구성 단위 (d) 및 상기 구성 단위 (a) ∼ (d) 이외의 구성 단위 (e) 를 추가로 함유하고,[16] The copolymer (A) further contains a structural unit (d) having a hydroxyl group and a structural unit (e) other than the structural units (a) to (d),
상기 공중합체 (A) 가, 상기 블록 이소시아나토기를 갖는 구성 단위 (a) 를 3 ∼ 20 몰%, 상기 산기를 갖는 구성 단위 (b) 를 20 ∼ 50 몰%, 상기 에폭시기를 갖는 구성 단위 (c) 를 20 ∼ 40 몰%, 상기 수산기를 갖는 구성 단위 (d) 를 0 몰% 초과 ∼ 20 몰% 및 상기 구성 단위 (e) 를 20 ∼ 40 몰% 함유하는 [1] ∼ [5] 중 어느 하나에 기재된 공중합체.The copolymer (A) contains 3 to 20 mol% of the structural unit (a) having the block isocyanato group, 20 to 50 mol% of the structural unit (b) having the acid group, and the structural unit having the epoxy group [1] to [5] containing 20 to 40 mol% of (c), more than 0 mol% to 20 mol% of the structural unit (d) having the hydroxyl group, and 20 to 40 mol% of the structural unit (e) The copolymer according to any one of the above.
[17] [1] ∼ [16] 중 어느 하나에 기재된 공중합체 (A) 와, 용제 (B) 및 반응성 희석제 (C) 의 적어도 일방을 함유하는 것을 특징으로 하는 중합체 조성물.[17] A polymer composition characterized by containing the copolymer (A) according to any one of [1] to [16], and at least one of a solvent (B) and a reactive diluent (C).
[18] [1] ∼ [16] 중 어느 하나에 기재된 공중합체 (A), 용제 (B), 반응성 희석제 (C) 및 광 중합 개시제 (D) 를 함유하는 것을 특징으로 하는 감광성 수지 조성물.[18] A photosensitive resin composition characterized by containing the copolymer (A) according to any one of [1] to [16], a solvent (B), a reactive diluent (C), and a photopolymerization initiator (D).
[19] [1] ∼ [16] 중 어느 하나에 기재된 공중합체 (A), 용제 (B), 반응성 희석제 (C), 광 중합 개시제 (D) 및 착색제 (E) 를 함유하는 것을 특징으로 하는 컬러 필터용 감광성 수지 조성물.[19] Characterized by containing the copolymer (A) according to any one of [1] to [16], a solvent (B), a reactive diluent (C), a photopolymerization initiator (D) and a colorant (E) A photosensitive resin composition for color filters.
[20] 상기 공중합체 (A) 와 상기 반응성 희석제 (C) 의 합계량 100 질량부에 대하여, 상기 공중합체 (A) 가 10 ∼ 100 질량부, 상기 용제 (B) 가 30 ∼ 1,000 질량부, 상기 반응성 희석제 (C) 가 0 질량부 초과 ∼ 90 질량부, 상기 광 중합 개시제 (D) 가 0.1 ∼ 30 질량부, 상기 착색제 (E) 가 3 ∼ 80 질량부 함유되는 [19] 에 기재된 컬러 필터용 감광성 수지 조성물.[20] Based on 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C), the copolymer (A) is 10 to 100 parts by mass, the solvent (B) is 30 to 1,000 parts by mass, the above The color filter according to [19], wherein the reactive diluent (C) is greater than 0 to 90 parts by mass, the photopolymerization initiator (D) is 0.1 to 30 parts by mass, and the colorant (E) is 3 to 80 parts by mass. A photosensitive resin composition.
[21] 상기 용제 (B) 가, 수산기 함유 유기 용제를 포함하는 [19] 또는 [20] 에 기재된 컬러 필터용 감광성 수지 조성물.[21] The photosensitive resin composition for color filters according to [19] or [20], wherein the solvent (B) contains a hydroxyl group-containing organic solvent.
[22] 상기 착색제 (E) 가, 안료를 포함하는 [19] ∼ [21] 중 어느 하나에 기재된 컬러 필터용 감광성 수지 조성물.[22] The photosensitive resin composition for color filters according to any one of [19] to [21], wherein the colorant (E) contains a pigment.
[23] [19] ∼ [22] 중 어느 하나에 기재된 컬러 필터용 감광성 수지 조성물의 경화물로 이루어지는 착색 패턴을 갖는 것을 특징으로 하는 컬러 필터.[23] A color filter characterized by having a color pattern comprising a cured product of the photosensitive resin composition for color filters according to any one of [19] to [22].
[24] [23] 에 기재된 컬러 필터를 구비하는 것을 특징으로 하는 화상 표시 소자.[24] An image display element characterized by comprising the color filter according to [23].
[25] [19] ∼ [22] 중 어느 하나에 기재된 컬러 필터용 감광성 수지 조성물을 기판에 도포하고, 노광하고, 알칼리 현상한 후, 160 ℃ 이하의 온도에서 베이킹하여 착색 패턴을 형성하는 공정을 포함하는 것을 특징으로 하는 컬러 필터의 제조 방법.[25] A step of applying the photosensitive resin composition for a color filter according to any one of [19] to [22] to a substrate, exposing, alkali developing, and then baking at a temperature of 160 ° C. or less to form a colored pattern. A method for manufacturing a color filter comprising:
본 발명에 의하면, 현상성 및 보존 안정성이 양호함과 함께, 저온에서 경화시켜도 내용제성이 우수한 착색 패턴을 부여하는 컬러 필터용 감광성 수지 조성물, 및 그 감광성 수지 조성물의 조제에 유용한 공중합체를 제공할 수 있다.According to the present invention, it is possible to provide a photosensitive resin composition for a color filter which has good developability and storage stability and imparts a colored pattern having excellent solvent resistance even when cured at a low temperature, and a copolymer useful for preparing the photosensitive resin composition. can
또, 본 발명에 의하면, 내용제성이 우수한 착색 패턴을 갖는 컬러 필터 및 그 제조 방법 그리고 그 컬러 필터를 구비하는 화상 표시 소자를 제공할 수 있다.Moreover, according to this invention, the color filter which has a coloring pattern excellent in solvent resistance, its manufacturing method, and the image display element provided with the color filter can be provided.
<공중합체 (A)><Copolymer (A)>
본 발명의 공중합체 (A) 는, 블록 이소시아나토기를 갖는 구성 단위 (a), 산기를 갖는 구성 단위 (b) 및 에폭시기를 갖는 구성 단위 (c) 를 함유하는 것을 특징으로 한다.The copolymer (A) of the present invention is characterized by containing a structural unit (a) having a block isocyanato group, a structural unit (b) having an acid group, and a structural unit (c) having an epoxy group.
<블록 이소시아나토기를 갖는 구성 단위 (a)><Structural unit (a) having a block isocyanato group>
공중합체 (A) 가 함유하는 블록 이소시아나토기를 갖는 구성 단위 (a) 는, 블록 이소시아나토기 함유 모노머 유래의 구성 단위이다. 그 모노머로는, 에틸렌성 불포화 결합과 블록 이소시아나토기를 갖는 모노머 등, 예를 들어, 분자 중에 비닐기, (메트)아크릴로일옥시기 등을 갖는 이소시아네이트 화합물에 있어서의 이소시아나토기를, 블록제로 블록화한 화합물을 들 수 있다. 이소시아네이트 화합물과 블록제의 반응은, 용제의 존재 유무에 관계없이 실시할 수 있다. 용제를 사용하는 경우, 이소시아나토기에 대하여 불활성인 용제를 사용할 필요가 있다. 블록화 반응시에, 주석, 아연, 납 등의 유기 금속염, 3 급 아민 등을 촉매로서 사용해도 된다. 반응은, 일반적으로 -20 ∼ 150 ℃ 에서 실시할 수 있지만, 0 ∼ 100 ℃ 에서 실시하는 것이 바람직하다. 상기한 이소시아네이트 화합물의 예로는, 하기 식 (1) 로 나타내는 화합물을 들 수 있다.The structural unit (a) containing a block isocyanato group contained in the copolymer (A) is a structural unit derived from a monomer containing a block isocyanato group. Examples of the monomer include a monomer having an ethylenically unsaturated bond and a block isocyanato group, for example, an isocyanato group in an isocyanate compound having a vinyl group, a (meth)acryloyloxy group, etc. in the molecule; The compound block|blocked by the blocking agent is mentioned. Reaction of an isocyanate compound and a blocking agent can be performed regardless of the presence or absence of a solvent. When using a solvent, it is necessary to use a solvent that is inactive with respect to the isocyanato group. In the case of blocking reaction, you may use organometallic salts, such as tin, zinc, and lead, tertiary amine, etc. as a catalyst. The reaction can generally be carried out at -20 to 150°C, but is preferably carried out at 0 to 100°C. As an example of said isocyanate compound, the compound represented by following formula (1) is mentioned.
[화학식 1][Formula 1]
상기 식 (1) 중, R1 은, 수소 원자 또는 메틸기를 나타내고, R2 는, -CO-, -COOR3- (여기서, R3 은 탄소 원자수 1 ∼ 6 의 알킬렌기이다) 또는 -COO-R4O-CONH-R5- (여기서, R4 는 탄소 원자수 2 ∼ 6 의 알킬렌기이고, R5 는 치환기를 가지고 있어도 되는 탄소 원자수 2 ∼ 12 의 알킬렌기 또는 탄소 원자수 6 ∼ 12 의 아릴렌기이다) 를 나타낸다. R2 는, 바람직하게는 -COOR3- 이고, 여기서, R3 은, 바람직하게는 탄소 원자수 1 ∼ 4 의 알킬렌기이다.In the above formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 is -CO-, -COOR 3 - (where R 3 is an alkylene group having 1 to 6 carbon atoms) or -COO -R 4 O-CONH-R 5 - (Here, R 4 is an alkylene group of 2 to 6 carbon atoms, and R 5 is an alkylene group of 2 to 12 carbon atoms which may have a substituent or 6 to 6 carbon atoms 12 arylene group). R 2 is preferably -COOR 3 -, wherein R 3 is preferably an alkylene group of 1 to 4 carbon atoms.
상기 식 (1) 로 나타내는 이소시아네이트 화합물로는, 구체적으로는, 2-이소시아나토에틸(메트)아크릴레이트, 2-이소시아나토프로필(메트)아크릴레이트, 3-이소시아나토프로필(메트)아크릴레이트, 2-이소시아나토-1-메틸에틸(메트)아크릴레이트, 2-이소시아나토-1,1-디메틸에틸(메트)아크릴레이트, 4-이소시아나토시클로헥실(메트)아크릴레이트, 메타크릴로일이소시아네이트 등을 들 수 있다. 또, 2-하이드록시알킬(메트)아크릴레이트와 디이소시아네이트 화합물의 등몰 (1 몰 : 1 몰) 반응 생성물도 사용할 수 있다. 상기한 2-하이드록시알킬(메트)아크릴레이트의 알킬기로는, 에틸기 또는 n-프로필기가 바람직하고, 에틸기가 보다 바람직하다. 상기한 디이소시아네이트 화합물로는, 예를 들어, 헥사메틸렌디이소시아네이트, 2,4- (또는 2,6-) 톨릴렌디이소시아네이트 (TDI), 4,4'-디페닐메탄디이소시아네이트 (MDI), 3,5,5-트리메틸-3-이소시아나토메틸시클로헥실이소시아네이트 (IPDI), m- (또는 p-) 자일렌디이소시아네이트, 1,3- (또는 1,4-) 비스(이소시아나토메틸)시클로헥산, 리신디이소시아네이트 등을 들 수 있다.As an isocyanate compound represented by said formula (1), specifically, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate Rate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, meta Chryloyl isocyanate etc. are mentioned. In addition, an equimolar (1 mol: 1 mol) reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. As the alkyl group of the 2-hydroxyalkyl (meth)acrylate described above, an ethyl group or an n-propyl group is preferable, and an ethyl group is more preferable. Examples of the above diisocyanate compounds include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3 ,5,5-trimethyl-3-isocyanatomethylcyclohexylisocyanate (IPDI), m- (or p-) xylene diisocyanate, 1,3- (or 1,4-) bis (isocyanatomethyl) cyclo Hexane, lysine diisocyanate, etc. are mentioned.
이들 이소시아네이트 화합물 중에서도, 2-이소시아나토에틸(메트)아크릴레이트, 2-이소시아나토프로필(메트)아크릴레이트, 3-이소시아나토프로필(메트)아크릴레이트, 2-이소시아나토-1-메틸에틸(메트)아크릴레이트, 2-이소시아나토-1,1-디메틸에틸(메트)아크릴레이트, 4-이소시아나토시클로헥실(메트)아크릴레이트 및 메타크릴로일이소시아네이트가 바람직하고, 2-이소시아나토에틸(메트)아크릴레이트 및 2-이소시아나토프로필(메트)아크릴레이트가 보다 바람직하다.Among these isocyanate compounds, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methyl Ethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate and methacryloylisocyanate are preferred, and 2-iso Cyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are more preferred.
또한, 본 명세서에 있어서 (메트)아크릴레이트라고 표기한 것은, 아크릴레이트 및 메타크릴레이트의 어느 것이어도 되는 것을 의미하고 있고, 또, (메트)아크릴산의 표기는 아크릴산 및 메타크릴산의 어느 것이어도 되는 것을 의미하고 있다.In addition, what is written as (meth)acrylate in this specification means that either of acrylate and methacrylate may be used, and the notation of (meth)acrylic acid may be either of acrylic acid or methacrylic acid. means to become
이소시아네이트 화합물에 있어서의 이소시아나토기를 블록화하는 블록제로는, 예를 들어, ε-카프로락탐, δ-발레로락탐, γ-부티로락탐, β-프로피오락탐 등의 락탐계 ; 메탄올, 에탄올, 프로판올, 부탄올, 에틸렌글리콜, 메틸셀로솔브, 부틸셀로솔브, 메틸카르비톨, 벤질알코올, 페닐셀로솔브, 푸르푸릴알코올, 시클로헥산올 등의 알코올계 ; 페놀, 크레졸, 2,6-자일레놀, 3,5-자일레놀, 에틸페놀, o-이소프로필페놀, p-tert-부틸페놀 등의 부틸페놀, p-tert-옥틸페놀, 노닐페놀, 디노닐페놀, 스티렌화페놀, 2-하이드록시벤조산메틸, 4-하이드록시벤조산메틸, 티몰, p-나프톨, p-니트로페놀, p-클로로페놀 등의 페놀계 ; 말론산디메틸, 말론산디에틸, 아세토아세트산메틸, 아세토아세트산에틸, 아세틸아세톤 등의 활성 메틸렌계 ; 부틸메르캅탄, 티오페놀, tert-도데실메르캅탄 등의 메르캅탄계 ; 디페닐아민, 페닐나프틸아민, 아닐린, 카르바졸 등의 아민계 ; 아세트아닐리드, 아세트아니시디드, 아세트산아미드, 벤즈아미드 등의 산아미드계 ; 숙신산이미드, 말레산이미드 등의 산이미드계 ; 이미다졸, 2-메틸이미다졸, 2-에틸이미다졸 등의 이미다졸계 ; 피라졸, 3,5-디메틸피라졸 등의 피라졸계 ; 우레아, 티오우레아, 에틸렌우레아 등의 우레아계 ; N-페닐카르바민산페닐, 2-옥사졸리돈 등의 카르바미드산염계 : 에틸렌이민, 폴리에틸렌이민 등의 이민계 ; 포름알도옥심, 아세트알도옥심, 아세트옥심, 메틸에틸케토옥심, 메틸이소부틸케토옥심, 시클로헥사논옥심 등의 옥심계 ; 중아황산소다, 중아황산칼륨 등의 중아황산염계 등을 들 수 있다. 이들 블록제는, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.As a blocking agent which blocks the isocyanato group in an isocyanate compound, For example, Lactam system, such as epsilon caprolactam, delta-valerolactam, gamma-butyrolactam, and beta-propiolactam; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; butylphenols such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, phenols such as dinonyl phenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; Active methylene type, such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; mercaptan systems such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; amines such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; Acid amide systems, such as acetanilide, acetanisidide, acetic acid amide, and benzamide; acid imide systems such as succinic acid imide and maleic acid imide; Imidazole types, such as imidazole, 2-methylimidazole, and 2-ethylimidazole; pyrazoles such as pyrazole and 3,5-dimethylpyrazole; Urea type|system|group, such as urea, thiourea, and ethylene urea; Carbamidate systems such as phenyl N-phenylcarbamate and 2-oxazolidone: Imine systems such as ethyleneimine and polyethyleneimine; oxime systems such as formaldoxime, acetaldooxime, acetooxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; Bisulfite types, such as sodium bisulfite and potassium bisulfite, etc. are mentioned. These blocking agents may be used individually or may be used in combination of 2 or more type.
블록제는 반응성이 높은 이소시아나토기를 보호하고 있지만, 가열에 의해 블록 이소시아나토기가 해리하여 이소시아나토기가 재생된다. 본 발명에서는, 그 이소시아나토기가 공중합체 (A) 나 반응성 희석제 (C) 에 포함되는 반응성의 관능기, 즉, 산기나 원하는 바에 따라 포함되는 하이드록시기, 아미노기 등과 반응하여, 가교 밀도가 높은 경화물을 형성한다.Although the blocking agent protects the highly reactive isocyanato group, the blocked isocyanato group is dissociated by heating and the isocyanato group is regenerated. In the present invention, the isocyanato group reacts with the reactive functional group contained in the copolymer (A) or the reactive diluent (C), that is, an acid group or optionally a hydroxyl group, an amino group, etc., and the crosslinking density is high. form a cured product.
후술하는 컬러 필터용 감광성 수지 조성물의 저온 경화성이나 보존 안정성의 관점에서, 블록 이소시아나토기를 갖는 구성 단위 (a) 를 부여하는 모노머로는, 블록 이소시아나토기 함유 (메트)아크릴레이트를 사용하는 것이 바람직하다. 100 ℃ 에서 30 분 가열 처리한 경우의 그 블록 이소시아나토기의 해리율이 바람직하게는 5 ∼ 99 질량%, 보다 바람직하게는 8 ∼ 97 질량%, 가장 바람직하게는 10 ∼ 95 질량% 가 되는 블록 이소시아나토기 함유 (메트)아크릴레이트를 사용하는 것이 보다 바람직하다. 또한, 블록 이소시아나토기 함유 (메트)아크릴레이트의 블록 이소시아나토기의 해리율은, 그 블록 이소시아나토기 함유 (메트)아크릴레이트의 농도가 20 질량% 인 n-옥탄올 용액을 조제하고, 그 용액에 1 질량% 상당의 디부틸주석라우레이트 및 3 질량% 상당의 페노티아진 (중합 방지제) 을 첨가한 후, 100 ℃ 에서 30 분 가열한 후의 그 블록 이소시아나토기 함유 (메트)아크릴레이트의 질량 감소 비율을 HPLC 분석에 의해 측정한 값으로 한다. 해리율이 상기 범위인 블록 이소시아나토기 함유 (메트)아크릴레이트를 사용하면, 합성시의 공중합체의 안정성을 충분히 확보할 수 있고, 경화 도막 제작시의 베이킹 온도를 충분히 낮출 수 있고 경화 도막의 내용제성도 충분히 확보할 수 있다. 이와 같은 해리율을 갖는 블록 이소시아나토기 함유 (메트)아크릴레이트의 블록제로는, 말론산디에틸, 3,5-디메틸피라졸, 메틸에틸케토옥심, 2-하이드록시벤조산메틸, 4-하이드록시벤조산메틸, 3,5-자일레놀, γ-부티로락탐, 1-메톡시-2-프로판올, 2,6-디메틸페놀 및 디이소프로필아민을 들 수 있다. 이들 블록제 중에서도, 저온 경화성의 관점에서, 말론산디에틸, 3,5-디메틸피라졸, 메틸에틸케토옥심, 2-하이드록시벤조산메틸, 4-하이드록시벤조산메틸 및 3,5-자일레놀이 보다 바람직하다.From the viewpoint of the low-temperature curability and storage stability of the photosensitive resin composition for color filters described later, a block isocyanato group-containing (meth)acrylate is used as a monomer giving the structural unit (a) having a block isocyanato group. It is desirable to do The dissociation rate of the block isocyanato group in the case of heat treatment at 100 ° C. for 30 minutes is preferably 5 to 99% by mass, more preferably 8 to 97% by mass, and most preferably 10 to 95% by mass. It is more preferable to use a (meth)acrylate containing a block isocyanato group. In addition, the dissociation rate of the block isocyanato group of the block isocyanato group-containing (meth)acrylate is determined by preparing an n-octanol solution in which the concentration of the block isocyanato group-containing (meth)acrylate is 20% by mass After adding 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (polymerization inhibitor) to the solution, the block isocyanato group-containing after heating at 100 ° C. for 30 minutes (meth) ) Let the mass reduction rate of acrylate be the value measured by HPLC analysis. When a block isocyanato group-containing (meth)acrylate having a dissociation rate in the above range is used, the stability of the copolymer at the time of synthesis can be sufficiently secured, the baking temperature at the time of producing a cured coating film can be sufficiently lowered, and the cured coating film The solvent resistance can also be sufficiently secured. Blocking agents for (meth)acrylates containing a blocked isocyanato group having such a dissociation rate include diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 2-hydroxybenzoate, and 4-hydroxyl. methyl benzoate, 3,5-xylenol, γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol and diisopropylamine. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate and 3,5-xylenol are preferred from the viewpoint of low-temperature curing properties. desirable.
또, 블록 이소시아나토기 함유 (메트)아크릴레이트의 블록 이소시아나토기의 해리 온도가 80 ℃ 이상인 블록 이소시아나토기 함유 (메트)아크릴레이트를 사용하는 것도 바람직하다. 해리 온도가 80 ℃ 이상인 블록 이소시아나토기 함유 (메트)아크릴레이트를 사용하면, 합성시의 공중합체의 안정성을 충분히 확보할 수 있고, 후술하는 변성 반응시에 의도하지 않은 가교 반응을 저감시킬 수 있다. 한편, 블록 이소시아나토기의 해리 온도가 160 ℃ 이하이면, 베이킹 온도를 충분히 낮출 수 있고 경화 도막의 내용제성도 충분히 확보할 수 있다. 또한, 블록 이소시아나토기 함유 (메트)아크릴레이트의 블록 이소시아나토기의 해리 온도는, 그 블록 이소시아나토기 함유 (메트)아크릴레이트의 농도가 20 질량% 인 n-옥탄올 용액을 조제하고, 그 용액에 1 질량% 상당의 디부틸주석라우레이트 및 3 질량% 상당의 페노티아진 (중합 방지제) 을 첨가한 후, 소정의 온도에서 가열하고, 30 분 후의 그 블록 이소시아나토기 함유 (메트)아크릴레이트의 질량 감소 비율을 HPLC 분석에 의해 측정하고, 그 질량 감소 비율이 80 질량% 이상이 되는 온도를 블록 이소시아나토기의 해리 온도로 한다.Moreover, it is also preferable to use block isocyanato group-containing (meth)acrylate whose dissociation temperature of the block isocyanato group of a block isocyanato group-containing (meth)acrylate is 80 degreeC or more. When a block isocyanato group-containing (meth)acrylate having a dissociation temperature of 80 ° C. or higher is used, stability of the copolymer during synthesis can be sufficiently secured, and unintended crosslinking reaction can be reduced during the denaturation reaction described later. there is. On the other hand, if the dissociation temperature of a block isocyanato group is 160 degreeC or less, baking temperature can fully be lowered and the solvent resistance of a cured coating film can also fully be ensured. In addition, the dissociation temperature of the block isocyanato group of the block isocyanato group-containing (meth)acrylate prepares an n-octanol solution in which the concentration of the block isocyanato group-containing (meth)acrylate is 20% by mass 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (a polymerization inhibitor) were added to the solution, followed by heating at a predetermined temperature, and containing the block isocyanato group after 30 minutes. The mass reduction rate of (meth)acrylate is measured by HPLC analysis, and the temperature at which the mass reduction rate becomes 80% by mass or more is the dissociation temperature of the block isocyanato group.
상기한 블록 이소시아나토기 함유 (메트)아크릴레이트의 예로는, 하기 식 (2) 로 나타내는 카렌즈 (등록상표) MOI-DEM (메타크릴로일옥시에틸이소시아네이트와 말론산디에틸의 반응 생성물, 쇼와 전공 주식회사 제조, 블록 이소시아나토기의 해리 온도 : 90 ℃, 해리율 : 90 질량%), 하기 식 (3) 으로 나타내는 카렌즈 MOI-BP (메타크릴로일옥시에틸이소시아네이트와 3,5-디메틸피라졸의 반응 생성물, 쇼와 전공 주식회사 제조, 블록 이소시아나토기의 해리 온도 : 110 ℃, 해리율 : 70 질량%), 하기 식 (4) 로 나타내는 카렌즈 MOI-BM (메타크릴로일옥시에틸이소시아네이트와 메틸에틸케토옥심의 반응 생성물, 쇼와 전공 주식회사 제조, 블록 이소시아나토기의 해리 온도 : 130 ℃, 해리율 : 18 질량%) 과 같은 메타크릴레이트 및 이들에 대응하는 아크릴레이트 등을 들 수 있다. 이들 블록 이소시아나토기 함유 (메트)아크릴레이트는, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.An example of the block isocyanato group-containing (meth)acrylate described above is Karenz (registered trademark) MOI-DEM (reaction product of methacryloyloxyethyl isocyanate and diethyl malonate, shown by the following formula (2)) Manufactured by Wa Denko Co., Ltd., dissociation temperature of block isocyanato group: 90 ° C., dissociation rate: 90 mass%), Karenz MOI-BP represented by the following formula (3) (methacryloyloxyethyl isocyanate and 3,5- Reaction product of dimethylpyrazole, manufactured by Showa Denko Co., Ltd., dissociation temperature of block isocyanato group: 110 ° C., dissociation rate: 70% by mass), Karenz MOI-BM represented by the following formula (4) (methacryloyl Methacrylates such as reaction products of oxyethyl isocyanate and methyl ethyl ketoxime, manufactured by Showa Electric Co., Ltd., dissociation temperature of block isocyanato group: 130°C, dissociation rate: 18% by mass) and acrylates corresponding thereto, and the like can be heard These block isocyanato group-containing (meth)acrylates may be used alone or in combination of two or more.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
공중합체 (A) 가 함유하는 블록 이소시아나토기를 갖는 구성 단위 (a) 의 비율은, 특별히 제한은 없지만, 바람직하게는 1 ∼ 40 몰%, 보다 바람직하게는 2 ∼ 30 몰%, 가장 바람직하게는 3 ∼ 25 몰% 이다. 블록 이소시아나토기를 갖는 구성 단위 (a) 의 비율이 1 ∼ 40 몰% 이면, 경화 도막의 내용제성이 개선되고, 공중합체 (A) 의 보존 안정성도 유지된다.The proportion of the structural unit (a) having a block isocyanato group contained in the copolymer (A) is not particularly limited, but is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, most preferably It is preferably 3 to 25 mol%. When the ratio of the structural unit (a) having a block isocyanato group is 1 to 40 mol%, the solvent resistance of the cured coating film is improved, and the storage stability of the copolymer (A) is also maintained.
<산기를 갖는 구성 단위 (b)><Structural unit (b) having an acid group>
공중합체 (A) 가 함유하는 산기를 갖는 구성 단위 (b) 는, 산기 함유 모노머 유래의 구성 단위이다 (단, 상기 블록 이소시아나토기를 갖는 구성 단위 (a) 에 해당하는 것은 제외한다). 산기로는, 카르복실기, 술포기, 포스포기 등을 들 수 있고, 이들 중에서도, 입수 용이성의 면에서 카르복실기가 바람직하다. 산기를 갖는 구성 단위 (b) 를 부여하는 모노머로는, 중합성 불포화 결합과 산기를 갖는 모노머, 예를 들어, 불포화 카르복실산 또는 그 무수물, 불포화 술폰산, 불포화 포스폰산 등을 들 수 있다. 바람직한 모노머의 구체예로는, (메트)아크릴산, α-브로모(메트)아크릴산, β-푸릴(메트)아크릴산, 크로톤산, 프로피올산, 신남산, α-시아노신남산, 말레산, 무수 말레산, 말레산모노메틸, 말레산모노에틸, 말레산모노이소프로필, 푸마르산, 이타콘산, 무수 이타콘산, 시트라콘산, 무수 시트라콘산 등의 불포화 카르복실산 또는 그 무수물 ; 2-아크릴아미드-2-메틸프로판술폰산, tert-부틸아크릴아미드술폰산, p-스티렌술폰산 등의 불포화 술폰산 ; 비닐포스폰산 등의 불포화 포스폰산 ; 등을 들 수 있다. 이들 모노머는, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다. 이들 중에서도, 알칼리 현상성이 우수한 점 및 입수 용이성의 관점에서, 불포화 카르복실산이 바람직하고, (메트)아크릴산이 보다 바람직하다.The structural unit (b) containing an acidic radical contained in the copolymer (A) is a structural unit derived from a monomer containing an acidic radical (except for structural units (a) having a block isocyanato group). As an acidic group, a carboxyl group, a sulfo group, a phospho group, etc. are mentioned, Among these, a carboxyl group is preferable from the point of availability. As a monomer giving the structural unit (b) which has an acid group, the monomer which has a polymerizable unsaturated bond and an acid group, for example, unsaturated carboxylic acid or its anhydride, unsaturated sulfonic acid, unsaturated phosphonic acid, etc. are mentioned. Specific examples of preferred monomers include (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, maleic acid and maleic anhydride. unsaturated carboxylic acids or anhydrides thereof such as acids, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; unsaturated sulfonic acids such as 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, and p-styrenesulfonic acid; unsaturated phosphonic acids such as vinylphosphonic acid; etc. can be mentioned. These monomers may be used individually or may be used in combination of 2 or more type. Among these, from the viewpoint of excellent alkali developability and ease of availability, unsaturated carboxylic acids are preferred, and (meth)acrylic acid is more preferred.
본 발명에서는, 산기를 갖는 구성 단위 (b) 가 공중합체 (A) 에 포함됨으로써, 공중합체 (A) 를 감광성 재료로서 사용할 때의 알칼리 현상성이 크게 개선된다.In the present invention, the alkali developability at the time of using the copolymer (A) as a photosensitive material is greatly improved by including the structural unit (b) having an acid group in the copolymer (A).
공중합체 (A) 가 함유하는 산기를 갖는 구성 단위 (b) 의 비율은, 특별히 제한은 없지만, 바람직하게는 1 ∼ 60 몰%, 보다 바람직하게는 10 ∼ 50 몰%, 가장 바람직하게는 15 ∼ 40 몰% 이다. 산기를 갖는 구성 단위 (b) 의 비율이 1 ∼ 60 몰% 이면, 적당한 알칼리 현상의 속도가 되고, 정밀한 패턴의 형성이 가능해진다.The proportion of the structural unit (b) having an acid group contained in the copolymer (A) is not particularly limited, but is preferably 1 to 60 mol%, more preferably 10 to 50 mol%, and most preferably 15 to 60 mol%. 40 mol%. When the ratio of the structural unit (b) having an acid group is 1 to 60 mol%, an appropriate alkali development rate is achieved, and formation of a precise pattern becomes possible.
<에폭시기를 갖는 구성 단위 (c)><Structural unit (c) having an epoxy group>
공중합체 (A) 가 함유하는 에폭시기를 갖는 구성 단위 (c) 는, 에폭시기 함유 모노머 유래의 구성 단위이다 (단, 상기 블록 이소시아나토기를 갖는 구성 단위 (a), 상기 산기를 갖는 구성 단위 (b) 에 해당하는 것은 제외한다). 에폭시기를 갖는 구성 단위 (c) 를 부여하는 모노머로는, 중합성 불포화 결합과 에폭시기를 갖는 모노머, 예를 들어, 옥시라닐(메트)아크릴레이트, 글리시딜(메트)아크릴레이트, 2-메틸글리시딜(메트)아크릴레이트, 2-에틸글리시딜(메트)아크릴레이트, 2-옥시라닐에틸(메트)아크릴레이트, 2-글리시딜옥시에틸(메트)아크릴레이트, 3-글리시딜옥시프로필(메트)아크릴레이트, 글리시딜옥시페닐(메트)아크릴레이트 등의 에폭시기를 포함하는 (메트)아크릴산에스테르 유도체 ; 3,4-에폭시시클로헥실(메트)아크릴레이트, 3,4-에폭시시클로헥실메틸(메트)아크릴레이트, 2-(3,4-에폭시시클로헥실)에틸(메트)아크릴레이트, 2-(3,4-에폭시시클로헥실메틸옥시)에틸(메트)아크릴레이트, 3-(3,4-에폭시시클로헥실메틸옥시)프로필(메트)아크릴레이트 등의 3,4-에폭시시클로헥산 고리 등의 에폭시기 함유 지환식 탄소 고리를 포함하는 (메트)아크릴산에스테르 유도체 ; 에폭시기를 포함하는 비닐에테르 화합물 ; 에폭시기를 포함하는 알릴에테르 화합물 등을 들 수 있다. 이들 모노머는, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다. 이들 중에서도, 중합성 및 입수 용이성의 관점에서, 옥시라닐(메트)아크릴레이트, 글리시딜(메트)아크릴레이트, 2-메틸글리시딜(메트)아크릴레이트, 2-에틸글리시딜(메트)아크릴레이트, 2-옥시라닐에틸(메트)아크릴레이트, 2-글리시딜옥시에틸(메트)아크릴레이트, 3-글리시딜옥시프로필(메트)아크릴레이트, 글리시딜옥시페닐(메트)아크릴레이트 등의 에폭시기 함유 (메트)아크릴레이트가 바람직하고, 글리시딜(메트)아크릴레이트가 보다 바람직하다.The structural unit (c) having an epoxy group contained in the copolymer (A) is a structural unit derived from an epoxy group-containing monomer (provided that the structural unit (a) having the block isocyanato group and the structural unit having the acid group ( b) is excluded). As the monomer giving the constituent unit (c) having an epoxy group, a monomer having a polymerizable unsaturated bond and an epoxy group, for example, oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglyc Cidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxy (meth)acrylic acid ester derivatives containing an epoxy group such as propyl (meth)acrylate and glycidyloxyphenyl (meth)acrylate; 3,4-epoxycyclohexyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl(meth)acrylate, 2-(3, Epoxy group-containing alicyclics such as 3,4-epoxycyclohexane rings such as 4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate (meth)acrylic acid ester derivatives containing a carbon ring; Vinyl ether compound containing an epoxy group; An allyl ether compound containing an epoxy group, etc. are mentioned. These monomers may be used individually or may be used in combination of 2 or more type. Among these, from the viewpoint of polymerizability and availability, oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth) Acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, glycidyloxyphenyl (meth)acrylate Epoxy group-containing (meth)acrylates such as the like are preferable, and glycidyl (meth)acrylate is more preferable.
본 발명에서는, 에폭시기를 갖는 구성 단위 (c) 가 공중합체 (A) 에 포함됨으로써, 공중합체 (A) 를 감광성 재료로서 사용할 때의 내용제성이 크게 개선된다.In the present invention, the solvent resistance at the time of using the copolymer (A) as a photosensitive material is greatly improved by including the structural unit (c) having an epoxy group in the copolymer (A).
공중합체 (A) 가 함유하는 에폭시기를 갖는 구성 단위 (c) 의 비율은, 특별히 제한은 없지만, 바람직하게는 1 ∼ 60 몰%, 보다 바람직하게는 5 ∼ 50 몰%, 가장 바람직하게는 10 ∼ 40 몰% 이다. 에폭시기를 갖는 구성 단위 (c) 의 비율이 1 ∼ 60 몰% 이면, 경화 도막의 내용제성과 공중합체 (A) 의 보존 안정성이 양립된다.The proportion of the structural unit (c) having an epoxy group contained in the copolymer (A) is not particularly limited, but is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and most preferably 10 to 60 mol%. 40 mol%. When the ratio of the constituent unit (c) having an epoxy group is 1 to 60 mol%, the solvent resistance of the cured coating film and the storage stability of the copolymer (A) are compatible.
공중합체 (A) 에 있어서, 블록 이소시아나토기를 갖는 구성 단위 (a) 와 에폭시를 갖는 구성 단위 (c) 의 몰비율은, 예를 들어, 1 : 99 ∼ 99 : 1 일 수 있고, 경화 도막의 내용제성 및 공중합체 (A) 의 보존 안정성의 관점에서, 5 : 95 ∼ 85 : 15 인 것이 바람직하고, 10 : 90 ∼ 75 : 25 인 것이 보다 바람직하다.In the copolymer (A), the molar ratio of the structural unit (a) having a block isocyanato group and the structural unit (c) having an epoxy may be, for example, 1:99 to 99:1, and curing From the viewpoint of the solvent resistance of the coating film and the storage stability of the copolymer (A), the ratio is preferably 5:95 to 85:15, and more preferably 10:90 to 75:25.
<수산기를 갖는 구성 단위 (d)><Structural unit (d) having a hydroxyl group>
공중합체 (A) 는, 수산기를 갖는 구성 단위 (d) 를 추가로 함유해도 된다. 공중합체 (A) 가 함유하는 수산기를 갖는 구성 단위 (d) 는, 수산기 함유 모노머 유래의 구성 단위이다 (단, 상기 블록 이소시아나토기를 갖는 구성 단위 (a), 상기 산기를 갖는 구성 단위 (b), 상기 에폭시기를 갖는 구성 단위 (c) 에 해당하는 것은 제외한다). 수산기를 갖는 구성 단위 (d) 를 부여하는 모노머로는, 중합성 불포화 결합과 수산기를 갖는 모노머, 예를 들어, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트, 2,3-디하이드록시프로필(메트)아크릴레이트, 2-하이드록시-3-페녹시프로필아크릴레이트, 4-하이드록시부틸아크릴레이트 등을 들 수 있다. 이들 모노머는, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다. 이들 중에서도, 중합성의 관점에서, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 2-하이드록시부틸(메트)아크릴레이트, 2,3-디하이드록시프로필(메트)아크릴레이트, 2-하이드록시-3-페녹시프로필아크릴레이트, 4-하이드록시부틸아크릴레이트 등의 수산기를 포함하는 (메트)아크릴산에스테르 유도체가 바람직하고, 2-하이드록시에틸(메트)아크릴레이트가 보다 바람직하다.The copolymer (A) may further contain a structural unit (d) having a hydroxyl group. The structural unit (d) having a hydroxyl group contained in the copolymer (A) is a structural unit derived from a monomer containing a hydroxyl group (however, the structural unit (a) having a block isocyanato group and the structural unit having an acid group ( b), those corresponding to the structural unit (c) having an epoxy group are excluded). As the monomer giving the structural unit (d) having a hydroxyl group, a monomer having a polymerizable unsaturated bond and a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate , 2-hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxybutyl acrylate and the like. there is. These monomers may be used individually or may be used in combination of 2 or more type. Among these, from a polymerizable viewpoint, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl ( (meth)acrylic acid ester derivatives containing a hydroxyl group such as meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate are preferable, and 2-hydroxyethyl (meth)acrylic acid rate is more preferred.
본 발명에서는, 수산기를 갖는 구성 단위 (d) 는 필수는 아니지만, 수산기를 갖는 구성 단위 (d) 가 공중합체 (A) 에 포함됨으로써, 공중합체 (A) 를 감광성 재료로서 사용할 때의 내용제성이 크게 개선된다.In the present invention, the structural unit (d) having a hydroxyl group is not essential, but when the copolymer (A) contains the structural unit (d) having a hydroxyl group, the solvent resistance at the time of using the copolymer (A) as a photosensitive material is improved. greatly improved
공중합체 (A) 가 함유하는 수산기를 갖는 구성 단위 (d) 의 비율은, 특별히 제한은 없지만, 바람직하게는 0 몰% 초과 ∼ 50 몰%, 보다 바람직하게는 0 몰% 초과 ∼ 40 몰%, 가장 바람직하게는 0 몰% 초과 ∼ 30 몰% 이다. 수산기를 갖는 구성 단위 (d) 의 비율이 0 몰% 초과 ∼ 50 몰% 이면, 경화 도막의 내용제성과 공중합체 (A) 의 보존 안정성이 양립된다.The ratio of the structural unit (d) having a hydroxyl group contained in the copolymer (A) is not particularly limited, but is preferably greater than 0 mol% to 50 mol%, more preferably greater than 0 mol% to 40 mol%, Most preferably, it is more than 0 mol% - 30 mol%. When the ratio of the structural unit (d) having a hydroxyl group is more than 0 mol% to 50 mol%, the solvent resistance of the cured coating film and the storage stability of the copolymer (A) are compatible.
<그 밖의 구성 단위 (e)><Other structural units (e)>
본 발명에 있어서는, 공중합체 (A) 가 함유하는 구성 단위로서, 블록 이소시아나토기를 갖는 구성 단위 (a), 산기를 갖는 구성 단위 (b), 에폭시기를 갖는 구성 단위 (c) 및 수산기를 갖는 구성 단위 (d) 와 함께, 이들과 공중합 가능한 그 밖의 구성 단위 (e) 가 함유되어도 된다 (단, 상기 블록 이소시아나토기를 갖는 구성 단위 (a), 상기 산기를 갖는 구성 단위 (b), 상기 에폭시기를 갖는 구성 단위 (c), 수산기를 갖는 구성 단위 (d) 에 해당하는 것은 제외한다). 그 밖의 구성 단위 (e) 를 부여하는 모노머의 구체예로는, 스티렌, α-메틸스티렌, o-비닐톨루엔, m-비닐톨루엔, p-비닐톨루엔, o-클로로스티렌, m-클로로스티렌, p-클로로스티렌, o-메톡시스티렌, m-메톡시스티렌, p-메톡시스티렌, p-니트로스티렌, p-시아노스티렌, p-아세틸아미노스티렌 등의 방향족 비닐 화합물 ; 노르보르넨(비시클로[2.2.1]헵트-2-엔), 5-메틸비시클로[2.2.1]헵트-2-엔, 5-에틸비시클로[2.2.1]헵트-2-엔, 테트라시클로[4.4.0.12,5.17,10]도데카-3-엔, 8-메틸테트라시클로[4.4.0.12,5.17,10]도데카-3-엔, 8-에틸테트라시클로[4.4.0.12,5.17,10]도데카-3-엔, 디시클로펜타디엔, 트리시클로[5.2.1.02,6]데카-8-엔, 트리시클로[5.2.1.02,6]데카-3-엔, 트리시클로[4.4.0.12,5]운데카-3-엔, 트리시클로[6.2.1.01,8]운데카-9-엔, 트리시클로[6.2.1.01,8]운데카-4-엔, 테트라시클로[4.4.0.12,5.17,10.01,6]도데카-3-엔, 8-메틸테트라시클로[4.4.0.12,5.17,10.01,6]도데카-3-엔, 8-에틸리덴테트라시클로[4.4.0.12,5.17,12]도데카-3-엔, 8-에틸리덴테트라시클로[4.4.0.12,5.17,10.01,6]도데카-3-엔, 펜타시클로[6.5.1.13,6.02,7.09,13]펜타데카-4-엔, 펜타시클로[7.4.0.12,5.19,12.08,13]펜타데카-3-엔 등의 노르보르넨 구조를 갖는 고리형 올레핀 ; 부타디엔, 이소프렌, 클로로프렌 등의 디엔 ; 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, n-프로필(메트)아크릴레이트, 이소-프로필(메트)아크릴레이트, n-부틸(메트)아크릴레이트, sec-부틸(메트)아크릴레이트, 이소-부틸(메트)아크릴레이트, tert-부틸(메트)아크릴레이트, 펜틸(메트)아크릴레이트, 네오펜틸(메트)아크릴레이트, 벤질(메트)아크릴레이트, 이소아밀(메트)아크릴레이트, 헥실(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, 라우릴(메트)아크릴레이트, 도데실(메트)아크릴레이트, 시클로펜틸(메트)아크릴레이트, 시클로헥실(메트)아크릴레이트, 메틸시클로헥실(메트)아크릴레이트, 에틸시클로헥실(메트)아크릴레이트, 1,4-시클로헥산디메탄올모노(메트)아크릴레이트, 로진(메트)아크릴레이트, 노르보르닐(메트)아크릴레이트, 5-메틸노르보르닐(메트)아크릴레이트, 5-에틸노르보르닐(메트)아크릴레이트, 디시클로펜테닐(메트)아크릴레이트, 디시클로펜타닐(메트)아크릴레이트, 디시클로펜테닐옥시에틸아크릴레이트이소보르닐(메트)아크릴레이트, 아다만틸(메트)아크릴레이트, 테트라하이드로푸르푸릴(메트)아크릴레이트, 1,1,1-트리플루오로에틸(메트)아크릴레이트, 퍼플루오로에틸(메트)아크릴레이트, 퍼플루오로-n-프로필(메트)아크릴레이트, 퍼플루오로-이소프로필(메트)아크릴레이트, 3-(N,N-디메틸아미노)프로필(메트)아크릴레이트, 트리페닐메틸(메트)아크릴레이트, 페닐(메트)아크릴레이트, 쿠밀(메트)아크릴레이트, 4-페녹시페닐(메트)아크릴레이트, 페녹시에틸(메트)아크릴레이트, 페녹시폴리에틸렌글리콜(메트)아크릴레이트, 노닐페녹시폴리에틸렌글리콜모노(메트)아크릴레이트, 비페닐옥시에틸(메트)아크릴레이트, 나프탈렌(메트)아크릴레이트, 안트라센(메트)아크릴레이트 등의 (메트)아크릴산에스테르 ; (메트)아크릴산아미드, (메트)아크릴산N,N-디메틸아미드, (메트)아크릴산N,N-디에틸아미드, (메트)아크릴산N,N-디프로필아미드, (메트)아크릴산N,N-디-이소프로필아미드, (메트)아크릴산안트라세닐아미드 등의 (메트)아크릴산아미드 ; (메트)아크릴산아닐리드, (메트)아크릴로니트릴, 아크롤레인, 염화비닐, 염화비닐리덴, 불화비닐, 불화비닐리덴, N-비닐피롤리돈, 비닐피리딘, 아세트산비닐, 비닐톨루엔 등의 비닐 화합물 ; 시트라콘산디에틸, 말레산디에틸, 푸마르산디에틸, 이타콘산디에틸 등의 불포화 디카르복실산디에스테르 ; N-페닐말레이미드, N-시클로헥실말레이미드, N-라우릴말레이미드, N-(4-하이드록시페닐)말레이미드 등의 모노말레이미드 ; 등을 들 수 있다. 이들 중에서도, (메트)아크릴산에스테르가 바람직하고, 메틸(메트)아크릴레이트 및 디시클로펜타닐(메트)아크릴레이트가 특히 바람직하다. 이들 모노머는, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.In this invention, as a structural unit which a copolymer (A) contains, the structural unit (a) which has a block isocyanato group, the structural unit (b) which has an acid group, the structural unit (c) which has an epoxy group, and a hydroxyl group Along with the structural unit (d), other structural units (e) copolymerizable with these may be contained (provided that the structural unit (a) having the block isocyanato group and the structural unit (b) having the acid group) , except those corresponding to the structural unit (c) having an epoxy group and the structural unit (d) having a hydroxyl group). Specific examples of the monomer giving the other structural unit (e) include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, and p -Aromatic vinyl compounds, such as chlorostyrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, p-nitro styrene, p-cyano styrene, and p-acetylamino styrene; Norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, Tetracyclo[4.4.0.1 2,5.1 7,10 ]dodeca-3-ene, 8-methyltetracyclo[4.4.0.1 2,5.1 7,10 ]dodeca-3-ene, 8-ethyl Tetracyclo[4.4.0.1 2,5.1 7,10 ]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 2,6 ]deca-8-ene, tricyclo[5.2.1.0 2 ,6 ]deca-3-ene, tricyclo[4.4.0.1 2,5 ]undeca-3-ene, tricyclo[6.2.1.0 1,8 ]undeca-9-ene, tricyclo[6.2.1.0 1 ,8 ]undeca-4-ene, tetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ]dodeca-3-ene, 8-methyltetracyclo[4.4.0.1 2,5 . 1 7,10 .0 1,6 ]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1 2,5.1 7,12 ]dodeca-3-ene, 8-ethylidenetetracyclo[ 4.4.0.1 2,5 .1 7,10 .0 1,6 ]dodeca-3-ene, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]pentadeca-4-ene Cyclic olefins having a norbornene structure such as pentacyclo[ 7.4.0.1 2,5.1 9,12.0 8,13 ]pentadeca-3-ene; dienes such as butadiene, isoprene, and chloroprene; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl ( meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-methylnor Bornyl(meth)acrylate, 5-ethylnorbornyl(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyloxyethyl acrylate isobornyl (meth)acrylate, adamantyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate , perfluoro-n-propyl (meth)acrylate, perfluoro-isopropyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, triphenylmethyl (meth)acrylate rate, phenyl (meth) acrylate, cumyl (meth) acrylate, 4-phenoxyphenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene (meth)acrylic acid esters such as glycol mono(meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth)acrylate, and anthracene (meth)acrylate; (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di - (meth)acrylic acid amides such as isopropylamide and (meth)acrylic acid anthracenylamide; vinyl compounds such as (meth)acrylic acid anilide, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene; Unsaturated dicarboxylic acid diesters, such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; etc. can be mentioned. Among these, (meth)acrylic acid esters are preferable, and methyl (meth)acrylate and dicyclopentanyl (meth)acrylate are particularly preferable. These monomers may be used individually or may be used in combination of 2 or more type.
공중합체 (A) 가 함유하는 그 밖의 구성 단위 (e) 의 비율은, 특별히 제한은 없지만, 바람직하게는 0 몰% 초과 ∼ 80 몰%, 보다 바람직하게는 5 ∼ 70 몰%, 가장 바람직하게는 10 ∼ 60 몰% 이다. 본 발명에서는, 그 밖의 구성 단위 (e) 는 필수는 아니지만, 그 밖의 구성 단위 (e) 가 공중합체 (A) 에 포함됨으로써, 내용제성, 도막의 특성을 적절히 향상시킬 수 있다.The proportion of the other constituent units (e) contained in the copolymer (A) is not particularly limited, but is preferably greater than 0 mol% to 80 mol%, more preferably 5 to 70 mol%, and most preferably It is 10-60 mol%. In the present invention, the other structural unit (e) is not essential, but solvent resistance and the characteristics of the coating film can be appropriately improved by including the other structural unit (e) in the copolymer (A).
<공중합체 (A) 의 제조 방법><Method for producing copolymer (A)>
공중합체 (A) 의 제조시에 사용되는 블록 이소시아나토기 함유 모노머 (a0), 산기 함유 모노머 (b0) 및 에폭시기 함유 모노머 (c0) 의 비율은, 특별히 제한은 없지만, 바람직하게는, (a0) 1 ∼ 60 몰%, (b0) 5 ∼ 65 몰% 및 (c0) 5 ∼ 65 몰%, 보다 바람직하게는, (a0) 5 ∼ 50 몰%, (b0) 15 ∼ 55 몰% 및 (c0) 15 ∼ 55 몰%, 가장 바람직하게는, (a0) 10 ∼ 40 몰%, (b0) 25 ∼ 45 몰% 및 (c0) 25 ∼ 45 몰% 이다. 공중합체 (A) 가 수산기를 갖는 구성 단위 (d) 및 그 밖의 구성 단위 (e) 를 추가로 함유하는 경우, 공중합체 (A) 의 제조시에 사용되는 블록 이소시아나토기 함유 모노머 (a0), 산기 함유 모노머 (b0), 에폭시기 함유 모노머 (c0), 수산기 함유 모노머 (d0) 및 그 밖의 모노머 (e0) 의 비율은, 바람직하게는, (a0) 1 ∼ 40 몰%, (b0) 1 ∼ 60 몰%, (c0) 1 ∼ 70 몰%, (d0) 0 몰% 초과 ∼ 50 몰% 및 (e0) 0 몰% 초과 ∼ 80 몰%, 보다 바람직하게는, (a0) 2 ∼ 30 몰%, (b0) 10 ∼ 55 몰%, (c0) 10 ∼ 60 몰%, (d0) 0 몰% 초과 ∼ 30 몰% 및 (e0) 5 ∼ 60 몰%, 가장 바람직하게는, (a0) 3 ∼ 20 몰%, (b0) 20 ∼ 50 몰%, (c0) 20 ∼ 40 몰%, (d0) 0 몰% 초과 ∼ 20 몰% 및 (e0) 20 ∼ 40 몰% 이다.The ratio of the block isocyanato group-containing monomer (a0), the acid group-containing monomer (b0) and the epoxy group-containing monomer (c0) used in the production of the copolymer (A) is not particularly limited, but preferably (a0 ) 1 to 60 mol%, (b0) 5 to 65 mol% and (c0) 5 to 65 mol%, more preferably (a0) 5 to 50 mol%, (b0) 15 to 55 mol% and (c0) ) 15 to 55 mol%, most preferably (a0) 10 to 40 mol%, (b0) 25 to 45 mol%, and (c0) 25 to 45 mol%. When the copolymer (A) further contains a structural unit (d) having a hydroxyl group and other structural units (e), a block isocyanato group-containing monomer (a0) used in the production of the copolymer (A) The ratio of the acid group-containing monomer (b0), the epoxy group-containing monomer (c0), the hydroxyl group-containing monomer (d0), and other monomers (e0) is preferably (a0) 1 to 40 mol%, (b0) 1 to 60 mol%, (c0) 1 to 70 mol%, (d0) more than 0 mol% to 50 mol%, and (e0) more than 0 mol% to 80 mol%, more preferably (a0) 2 to 30 mol% , (b0) 10 to 55 mol%, (c0) 10 to 60 mol%, (d0) greater than 0 mol% to 30 mol% and (e0) 5 to 60 mol%, most preferably (a0) 3 to 20 mol%, (b0) 20 to 50 mol%, (c0) 20 to 40 mol%, (d0) more than 0 mol% to 20 mol%, and (e0) 20 to 40 mol%.
블록 이소시아나토기 함유 모노머 (a0), 산기 함유 모노머 (b0), 에폭시기 함유 모노머 (c0), 수산기 함유 모노머 (d0) 및 그 밖의 모노머 (e0) 의 공중합 반응은, 당해 기술 분야에 있어서 공지된 라디칼 중합 방법에 따라서 중합 용제의 존재하 또는 부존재하에서 실시할 수 있다. 예를 들어, 이들 모노머를 원하는 바에 따라 용제에 용해시킨 후, 그 용액에 중합 개시제를 첨가하고, 50 ∼ 100 ℃ 에서 1 ∼ 20 시간에 걸쳐 중합 반응을 실시하면 된다. 이 때, 블록 이소시아나토기 함유 모노머 (a0) 의 블록 이소시아나토기가 해리하는 온도에서 중합 반응을 실시하면, 블록 이소시아나토기가 해리하여 발생하는 이소시아나토기가 산기와 반응하여 겔이 발생하기 때문에, 블록 이소시아나토기의 해리 온도를 하회하는 온도, 바람직하게는, 블록 이소시아나토기의 해리 온도를 20 ∼ 50 ℃ 정도 하회하는 온도에서 중합을 실시하는 것이 바람직하다.The copolymerization reaction of the block isocyanato group-containing monomer (a0), acid group-containing monomer (b0), epoxy group-containing monomer (c0), hydroxyl group-containing monomer (d0), and other monomers (e0) is known in the art. Depending on the radical polymerization method, it can be carried out in the presence or absence of a polymerization solvent. For example, after dissolving these monomers in a solvent as desired, a polymerization initiator may be added to the solution, and a polymerization reaction may be performed at 50 to 100°C for 1 to 20 hours. At this time, when the polymerization reaction is carried out at a temperature at which the block isocyanato group of the block isocyanato group-containing monomer (a0) dissociates, the isocyanato group generated by dissociation of the block isocyanato group reacts with the acid group to form a gel. Since this occurs, it is preferable to carry out the polymerization at a temperature lower than the dissociation temperature of the block isocyanato group, preferably at a temperature lower than the dissociation temperature of the block isocyanato group by about 20 to 50°C.
이 공중합 반응에 사용하는 것이 가능한 용제로는, 반응에 불활성이면 특별히 한정되지 않지만, 예를 들어, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노메틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노-n-프로필에테르, 디에틸렌글리콜모노-n-부틸에테르, 트리에틸렌글리콜모노메틸에테르, 트리에틸렌글리콜모노에틸에테르, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 디프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노에틸에테르, 디프로필렌글리콜모노-n-프로필에테르, 디프로필렌글리콜모노-n-부틸에테르, 트리프로필렌글리콜모노메틸에테르, 트리프로필렌글리콜모노에틸에테르 등의 (폴리)알킬렌글리콜모노알킬에테르류 ; 에틸렌글리콜모노메틸에테르아세테이트, 에틸렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트 등의 (폴리)알킬렌글리콜모노알킬에테르아세테이트류 ; 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜메틸에틸에테르, 디에틸렌글리콜디에틸에테르, 테트라하이드로푸란 등의 다른 에테르류 ; 메틸에틸케톤, 시클로헥사논, 2-헵타논, 3-헵타논 등의 케톤류 ; 2-하이드록시프로피온산메틸, 2-하이드록시프로피온산에틸, 2-하이드록시-2-메틸프로피온산메틸, 2-하이드록시-2-메틸프로피온산에틸, 3-메톡시프로피온산메틸, 3-메톡시프로피온산에틸, 3-에톡시프로피온산메틸, 3-에톡시프로피온산에틸, 에톡시아세트산에틸, 하이드록시아세트산에틸, 2-하이드록시-3-메틸부티르산메틸, 3-메틸-3-메톡시부틸아세테이트, 3-메틸-3-메톡시부틸프로피오네이트, 아세트산에틸, 아세트산n-부틸, 아세트산n-프로필, 아세트산i-프로필, 아세트산n-부틸, 아세트산i-부틸, 아세트산n-아밀, 아세트산i-아밀, 프로피온산n-부틸, 부티르산에틸, 부티르산n-프로필, 부티르산i-프로필, 부티르산n-부틸, 피루브산메틸, 피루브산에틸, 피루브산n-프로필, 아세토아세트산메틸, 아세토아세트산에틸, 2-옥소부티르산에틸 등의 에스테르류 ; 톨루엔, 자일렌 등의 방향족 탄화수소류 ; N-메틸피롤리돈, N,N-디메틸포름아미드, N,N-디메틸아세트아미드 등의 카르복실산아미드류 ; 디에틸렌글리콜 등을 들 수 있다. 이들 용제는, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.The solvent that can be used in this copolymerization reaction is not particularly limited as long as it is inactive to the reaction, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. , diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol (Poly)alkyl such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether len glycol monoalkyl ethers; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; 2-hydroxymethylpropionate, 2-hydroxyethylpropionate, 2-hydroxy-2-methylmethylpropionate, 2-hydroxy-2-methylethylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-Ethoxymethylpropionate, 3-ethoxyethylpropionate, ethoxyacetate ethyl, hydroxyacetate ethyl, 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, 3-methyl- 3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-propionic acid esters such as butyl, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; Aromatic hydrocarbons, such as toluene and xylene; carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide; Diethylene glycol etc. are mentioned. These solvents may be used individually or may be used in combination of 2 or more type.
이들 용제 중에서도, 에테르계 용제가 바람직하고, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노메틸에테르아세테이트, 디에틸렌글리콜메틸에틸에테르 및 에틸렌글리콜모노메틸에테르가 보다 바람직하다.Among these solvents, ether solvents are preferred, and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether and ethylene glycol monomethyl ether are more preferred.
공중합 반응에 사용하는 용제의 양은, 특별히 한정되지 않지만, 모노머의 주입량의 합계를 100 질량부로 한 경우에, 일반적으로 30 ∼ 1,000 질량부, 바람직하게는 50 ∼ 800 질량부이다. 특히, 용제의 양을 1,000 질량부 이하로 함으로써, 연쇄 이동 작용에 의한 공중합체 (A) 의 분자량의 저하를 억제하며, 또한 공중합체 (A) 의 점도를 적절한 범위로 제어할 수 있다. 또, 용제의 양을 30 질량부 이상으로 함으로써, 이상 중합 반응을 방지하고, 중합 반응을 안정적으로 실시할 수 있음과 함께, 공중합체 (A) 의 착색이나 겔화를 방지할 수도 있다.The amount of the solvent used in the copolymerization reaction is not particularly limited, but is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass, based on 100 parts by mass of the total amount of monomers charged. In particular, by setting the amount of the solvent to 1,000 parts by mass or less, the decrease in molecular weight of the copolymer (A) due to chain transfer action can be suppressed, and the viscosity of the copolymer (A) can be controlled within an appropriate range. Moreover, by making the quantity of a solvent into 30 mass parts or more, while being able to prevent an abnormal polymerization reaction and carrying out a polymerization reaction stably, coloring and gelation of a copolymer (A) can also be prevented.
또, 이 공중합 반응에 사용하는 것이 가능한 중합 개시제로는, 특별히 한정되지 않지만, 예를 들어, 아조비스이소부티로니트릴, 아조비스이소발레로니트릴, 과산화벤조일, t-부틸퍼옥시-2-에틸헥사노에이트 등을 들 수 있다. 이들 중합 개시제는, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다. 중합 개시제의 사용량은, 모노머의 전체 주입량을 100 질량부로 한 경우에, 일반적으로 0.5 ∼ 20 질량부, 바람직하게는 1.0 ∼ 10 질량부이다.In addition, the polymerization initiator that can be used for this copolymerization reaction is not particularly limited, but examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, and t-butylperoxy-2-ethyl Hexanoate etc. are mentioned. These polymerization initiators may be used individually or may be used in combination of 2 or more type. The usage amount of the polymerization initiator is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass, based on 100 parts by mass of the total amount of the monomers.
공중합체 (A) 의 폴리스티렌 환산의 중량 평균 분자량은, 특별히 제한되지 않지만, 상기한 제조 방법에 의해, 바람직하게는 1,000 ∼ 50,000, 보다 바람직하게는 3,000 ∼ 40,000 의 중량 평균 분자량을 갖는 공중합체 (A) 를 얻을 수 있다. 공중합체 (A) 의 중량 평균 분자량이 1,000 이상이면, 감광성 수지 조성물로서 사용할 때의 알칼리 현상 후에 착색 패턴의 결손이 잘 발생하지 않게 된다. 한편, 공중합체 (A) 의 중량 평균 분자량이 50,000 이하이면, 현상 시간이 적절해지고, 실용성이 확보된다.The weight average molecular weight of the copolymer (A) in terms of polystyrene is not particularly limited, but by the above production method, a copolymer having a weight average molecular weight of preferably 1,000 to 50,000, more preferably 3,000 to 40,000 (A ) can be obtained. When the weight average molecular weight of the copolymer (A) is 1,000 or more, the loss of the colored pattern hardly occurs after alkali development when used as a photosensitive resin composition. On the other hand, when the weight average molecular weight of the copolymer (A) is 50,000 or less, the development time becomes appropriate and practicality is ensured.
또, 공중합체 (A) 의 산가 (JIS K6901 5.3) 는, 적절히 선택할 수 있지만, 감광성 수지 조성물에 배합하는 경우에는, 바람직하게는 20 ∼ 300 KOHmg/g, 보다 바람직하게는 30 ∼ 200 KOHmg/g 의 범위이다. 공중합체 (A) 의 산가가 20 KOHmg/g 이상이면, 감광성 수지 조성물로서 사용할 때의 알칼리 현상성이 양호해진다. 한편, 공중합체 (A) 의 산가가 300 KOHmg/g 이하이면, 알칼리 현상액에 대하여 노광 부분 (광 경화 부분) 이 용해되기 어렵기 때문에, 패턴 형상이 양호해진다.The acid value (JIS K6901 5.3) of the copolymer (A) can be appropriately selected, but when blended in the photosensitive resin composition, it is preferably 20 to 300 KOHmg/g, more preferably 30 to 200 KOHmg/g is the range of When the acid value of the copolymer (A) is 20 KOHmg/g or more, the alkali developability at the time of use as a photosensitive resin composition becomes good. On the other hand, if the acid value of the copolymer (A) is 300 KOHmg/g or less, the exposed portion (photocured portion) is less likely to be dissolved in an alkali developing solution, so the pattern shape becomes good.
또한, 공중합체 (A) 의 에폭시 당량은, 특별히 제한되지 않지만, 바람직하게는 200 ∼ 2,000 g/mol, 보다 바람직하게는 300 ∼ 1500 g/mol, 가장 바람직하게는 480 ∼ 900 g/mol 의 범위이다. 공중합체 (A) 의 에폭시 당량이 200 g/mol 이상이면, 안정성이 양호해진다. 한편, 에폭시 당량이 2,000 g/mol 이하이면, 내용제성이 충분히 확보된다. 또한, 에폭시 당량이란, 중합체의 에폭시기 1 몰당 중합체의 질량이고, 중합체의 질량을 중합체의 에폭시기량으로 나눔으로써 구하는 것이 가능하다 (g/mol). 본 발명에 있어서, 에폭시 당량은, 에폭시기를 도입하기 위해 사용되는 원료의 주입량으로부터 계산한 이론치이다.In addition, the epoxy equivalent of the copolymer (A) is not particularly limited, but is preferably in the range of 200 to 2,000 g/mol, more preferably 300 to 1500 g/mol, and most preferably 480 to 900 g/mol. to be. Stability becomes favorable as the epoxy equivalent of copolymer (A) is 200 g/mol or more. On the other hand, when the epoxy equivalent is 2,000 g/mol or less, solvent resistance is sufficiently secured. In addition, an epoxy equivalent is the mass of a polymer per 1 mol of epoxy groups of a polymer, and can be calculated|required by dividing the mass of a polymer by the epoxy group weight of a polymer (g/mol). In the present invention, the epoxy equivalent is a theoretical value calculated from the injected amount of the raw material used for introducing the epoxy group.
본 발명의 공중합체 (A) 는, 분자 중에 블록 이소시아나토기를 포함하고 있다. 블록 이소시아나토기의 함유량은, 적절히 선택하면 되지만, 통상, 블록 이소시아나토기 당량이 400 ∼ 6,000, 바람직하게는 1,000 ∼ 5,000 이 되는 범위에서 선택된다. 블록 이소시아나토기 당량은, 중합체에 포함되는 블록 이소시아나토기 1 몰당 중합체의 질량이고, 중합체의 질량을 중합체에 포함되는 블록 이소시아나토기의 몰수로 나눔으로써 구하는 것이 가능하다 (g/mol). 본 발명에 있어서, 블록 이소시아나토기 당량은, 블록 이소시아나토기 함유 모노머의 주입량으로부터 계산한 이론치이다.The copolymer (A) of the present invention contains a block isocyanato group in its molecule. What is necessary is just to select content of a block isocyanato group suitably, but normally, a block isocyanato group equivalent is 400-6,000, Preferably it is selected in the range used as 1,000-5,000. The block isocyanato group equivalent is the mass of the polymer per mole of the block isocyanato group contained in the polymer, and can be obtained by dividing the mass of the polymer by the number of moles of the block isocyanato group contained in the polymer (g/mol ). In the present invention, the block isocyanato group equivalent is a theoretical value calculated from the preparation amount of the block isocyanato group-containing monomer.
<중합체 조성물><Polymer composition>
본 발명에 있어서는, 상기한 공중합체 (A) 에 더하여, 용제 (B) 및 반응성 희석제 (C) 의 적어도 일방을 포함하는 중합체 조성물이 제공된다. 용제 (B) 는, 공중합체 (A) 와 반응하지 않는 불활성인 용제이면 특별히 한정되지 않고, 공중합체 (A) 를 제조할 때에 사용한 용제와 동일한 범주의 것을 사용할 수 있다. 바람직한 용제 (B) 는, 이상 중합을 방지하고, 중합 반응을 안정적으로 실시할 수 있다는 관점에서, 프로필렌글리콜모노메틸에테르, 디에틸렌글리콜 등의 수산기 함유 유기 용제이다.In this invention, in addition to the copolymer (A) described above, a polymer composition containing at least one of a solvent (B) and a reactive diluent (C) is provided. The solvent (B) is not particularly limited as long as it is an inactive solvent that does not react with the copolymer (A), and a solvent of the same category as the solvent used when producing the copolymer (A) can be used. A preferable solvent (B) is a hydroxyl group-containing organic solvent, such as propylene glycol monomethyl ether and diethylene glycol, from the viewpoint of preventing abnormal polymerization and stably carrying out the polymerization reaction.
본 발명의 중합체 조성물은, 중합계로부터 단리한 공중합체 (A) 에 원하는 용제 (B) 를 적절히 혼합하여 조제할 수도 있지만, 반드시 공중합체 (A) 를 중합계로부터 단리할 필요는 없고, 공중합 반응 종료시에 포함되어 있는 용제를 그대로 사용할 수 있고, 그 때에 필요에 따라 원하는 용제를 더욱 추가할 수도 있다. 또, 중합체 조성물을 조제할 때에 사용되는 그 밖의 성분에 포함되어 있는 용제를, 용제 (B) 의 성분으로서 사용할 수도 있다.The polymer composition of the present invention may be prepared by appropriately mixing the desired solvent (B) with the copolymer (A) isolated from the polymerization system, but it is not always necessary to isolate the copolymer (A) from the polymerization system, and the copolymerization reaction The solvent contained at the end can be used as it is, and at that time, a desired solvent can also be further added as needed. Moreover, the solvent contained in the other components used when preparing a polymer composition can also be used as a component of solvent (B).
반응성 희석제 (C) 는, 분자 내에 중합성 관능기로서 적어도 하나의 중합 가능한 에틸렌성 불포화기를 갖는 화합물이고, 그 중에서도 중합성 관능기를 복수 갖는 화합물이 바람직하다. 이와 같은 반응성 희석제 (C) 를 공중합체 (A) 와 병용함으로써, 점도를 조정하거나, 형성되는 경화물의 강도나, 기재에 대한 밀착성을 향상시킬 수 있다.The reactive diluent (C) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule, and among these, a compound having a plurality of polymerizable functional groups is preferable. By using such a reactive diluent (C) in combination with the copolymer (A), the viscosity can be adjusted, the strength of the cured product formed, and the adhesion to the substrate can be improved.
반응성 희석제 (C) 로서 사용되는 단관능 모노머로는, (메트)아크릴아미드, 메틸올(메트)아크릴아미드, 메톡시메틸(메트)아크릴아미드, 에톡시메틸(메트)아크릴아미드, 프로폭시메틸(메트)아크릴아미드, 부톡시메톡시메틸(메트)아크릴아미드, 메틸(메트)아크릴레이트, 에틸(메트)아크릴레이트, 부틸(메트)아크릴레이트, 2-에틸헥실(메트)아크릴레이트, 2-하이드록시에틸(메트)아크릴레이트, 2-하이드록시프로필(메트)아크릴레이트, 4-하이드록시부틸(메트)아크릴레이트, 2-페녹시-2-하이드록시프로필(메트)아크릴레이트, 2-(메트)아크릴로일옥시-2-하이드록시프로필프탈레이트, 글리세린모노(메트)아크릴레이트, 테트라하이드로푸르푸릴(메트)아크릴레이트, 글리시딜(메트)아크릴레이트, 2,2,2-트리플루오로에틸(메트)아크릴레이트, 2,2,3,3-테트라플루오로프로필(메트)아크릴레이트, 프탈산 유도체의 하프(메트)아크릴레이트 등의 (메트)아크릴레이트류 ; 스티렌, α-메틸스티렌, α-클로로메틸스티렌, 비닐톨루엔 등의 방향족 비닐 화합물류 ; 아세트산비닐, 프로피온산비닐 등의 카르복실산에스테르류 등을 들 수 있다. 또, 이들 모노머는, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.As the monofunctional monomer used as the reactive diluent (C), (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl ( Meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxy Roxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acrylate ) Acryloyloxy-2-hydroxypropylphthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, glycidyl(meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylates such as (meth)acrylates, 2,2,3,3-tetrafluoropropyl (meth)acrylates, and half (meth)acrylates of phthalic acid derivatives; Aromatic vinyl compounds, such as styrene, (alpha)-methylstyrene, (alpha)-chloromethylstyrene, and vinyltoluene; and carboxylic acid esters such as vinyl acetate and vinyl propionate. Moreover, these monomers may be used independently and may be used in combination of 2 or more type.
반응성 희석제 (C) 로서 사용되는 다관능 모노머로는, 에틸렌글리콜디(메트)아크릴레이트, 디에틸렌글리콜디(메트)아크릴레이트, 테트라에틸렌글리콜디(메트)아크릴레이트, 프로필렌글리콜디(메트)아크릴레이트, 폴리프로필렌글리콜디(메트)아크릴레이트, 부틸렌글리콜디(메트)아크릴레이트, 네오펜틸글리콜디(메트)아크릴레이트, 1,6-헥산글리콜디(메트)아크릴레이트, 트리메틸올프로판트리(메트)아크릴레이트, 글리세린디(메트)아크릴레이트, 펜타에리트리톨디(메트)아크릴레이트, 펜타에리트리톨트리(메트)아크릴레이트, 디펜타에리트리톨펜타(메트)아크릴레이트, 디펜타에리트리톨헥사(메트)아크릴레이트, 2,2-비스(4-(메트)아크릴록시디에톡시페닐)프로판, 2,2-비스(4-(메트)아크릴록시폴리에톡시페닐)프로판, 2-하이드록시-3-(메트)아크릴로일옥시프로필(메트)아크릴레이트, 에틸렌글리콜디글리시딜에테르디(메트)아크릴레이트, 디에틸렌글리콜디글리시딜에테르디(메트)아크릴레이트, 프탈산디글리시딜에스테르디(메트)아크릴레이트, 글리세린트리아크릴레이트, 글리세린폴리글리시딜에테르폴리(메트)아크릴레이트, 우레탄(메트)아크릴레이트 (즉, 톨릴렌디이소시아네이트), 트리메틸헥사메틸렌디이소시아네이트와 헥사메틸렌디이소시아네이트 등과 2-하이드록시에틸(메트)아크릴레이트의 반응물, 트리스(하이드록시에틸)이소시아누레이트의 트리(메트)아크릴레이트 등의 (메트)아크릴레이트류 ; 디비닐벤젠, 디알릴프탈레이트, 디알릴벤젠포스포네이트 등의 방향족 비닐 화합물류 ; 아디프산디비닐 등의 디카르복실산에스테르류 ; 트리알릴시아누레이트, 메틸렌비스(메트)아크릴아미드, (메트)아크릴아미드메틸렌에테르, 다가 알코올과 N-메틸올(메트)아크릴아미드의 축합물 등을 들 수 있다. 이들 모노머는, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.Examples of the polyfunctional monomer used as the reactive diluent (C) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and propylene glycol di(meth)acrylate. rate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri( Meth) acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3 -(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. (meth)acrylates, such as a reaction product of 2-hydroxyethyl (meth)acrylate and tri(meth)acrylate of tris(hydroxyethyl)isocyanurate; aromatic vinyl compounds such as divinylbenzene, diallylphthalate, and diallylbenzenephosphonate; dicarboxylic acid esters such as divinyl adipate; triallyl cyanurate, methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, a condensate of a polyhydric alcohol and N-methylol(meth)acrylamide, and the like. These monomers may be used individually or may be used in combination of 2 or more type.
중합체 조성물에 있어서의 공중합체 (A), 용제 (B) 및 반응성 희석제 (C) 의 배합량은, 사용 목적에 따라 적절히 조정하면 된다. 중합체 조성물이, 공중합체 (A) 와 용제 (B) 와 반응성 희석제 (C) 를 포함하는 경우, 통상은, 공중합체 (A) 와 반응성 희석제 (C) 의 합계량 100 질량부에 대하여, 공중합체 (A) 가 10 ∼ 90 질량부, 용제 (B) 가 30 ∼ 1,000 질량부, 반응성 희석제 (C) 가 10 ∼ 90 질량부이고, 바람직하게는, 공중합체 (A) 가 20 ∼ 80 질량부, 용제 (B) 가 50 ∼ 800 질량부, 반응성 희석제 (C) 가 20 ∼ 80 질량부이고, 보다 바람직하게는, 공중합체 (A) 가 30 ∼ 75 질량부, 용제 (B) 가 100 ∼ 700 질량부, 반응성 희석제 (C) 가 25 ∼ 70 질량부이다. 이 범위의 배합량이면, 적절한 점도를 갖는 중합체 조성물이 되고, 후술하는 컬러 필터용 감광성 수지 조성물을 조제하기 위해 사용할 수 있는 것 외에, 각종 코팅, 접착제, 인쇄 잉크용 바인더 등에 사용하는 것도 가능하다.What is necessary is just to adjust the compounding quantity of the copolymer (A) in a polymer composition, a solvent (B), and a reactive diluent (C) suitably according to the purpose of use. When the polymer composition contains the copolymer (A), the solvent (B), and the reactive diluent (C), usually, the copolymer ( 10 to 90 parts by mass of A), 30 to 1,000 parts by mass of solvent (B), 10 to 90 parts by mass of reactive diluent (C), preferably 20 to 80 parts by mass of copolymer (A), solvent (B) is 50 to 800 parts by mass, the reactive diluent (C) is 20 to 80 parts by mass, more preferably, the copolymer (A) is 30 to 75 parts by mass, and the solvent (B) is 100 to 700 parts by mass , 25 to 70 parts by mass of the reactive diluent (C). A blending amount within this range results in a polymer composition having an appropriate viscosity, and can be used for preparing a photosensitive resin composition for color filters described later, as well as various coatings, adhesives, binders for printing inks, etc. It is also possible to use.
<감광성 수지 조성물><Photosensitive resin composition>
본 발명에 있어서는, 공중합체 (A), 용제 (B), 반응성 희석제 (C) 및 광 중합 개시제 (D) 를 함유하는 감광성 수지 조성물이 제공된다. 용제 (B) 및 반응성 희석제 (C) 로는, 상기한 것을 사용할 수 있다.In this invention, the photosensitive resin composition containing a copolymer (A), a solvent (B), a reactive diluent (C), and a photoinitiator (D) is provided. As the solvent (B) and the reactive diluent (C), those described above can be used.
광 중합 개시제 (D) 로는, 특별히 한정되지 않지만, 예를 들어, 벤조인, 벤조인메틸에테르, 벤조인에틸에테르, 벤조인부틸에테르 등의 벤조인류 ; 아세토페논, 2,2-디메톡시-2-페닐아세토페논, 1,1-디클로로아세토페논, 4-(1-t-부틸디옥시-1-메틸에틸)아세토페논, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노-프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)부타논-1 등의 아세토페논류 ; 2-메틸안트라퀴논, 2-아밀안트라퀴논, 2-t-부틸안트라퀴논, 1-클로로안트라퀴논 등의 안트라퀴논류 ; 크산톤, 티오크산톤, 2,4-디메틸티오크산톤, 2,4-디이소프로필티오크산톤, 2-클로로티오크산톤 등의 티오크산톤류 ; 아세토페논디메틸케탈, 벤질디메틸케탈 등의 케탈류 ; 벤조페논, 4-(1-t-부틸디옥시-1-메틸에틸)벤조페논, 3,3',4,4'-테트라키스(t-부틸디옥시카르보닐)벤조페논 등의 벤조페논류 ; 아실포스핀옥사이드류 ; 등을 들 수 있다. 이들 광 중합 개시제 (D) 는, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.Although it does not specifically limit as a photoinitiator (D), For example, Benzoins, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl-1-[ acetophenones such as 4-(methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthone such as xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone ; acyl phosphine oxides; etc. can be mentioned. These photoinitiators (D) may be used independently or may be used in combination of 2 or more type.
<컬러 필터용 감광성 수지 조성물><Photosensitive resin composition for color filters>
본 발명에 있어서는, 공중합체 (A), 용제 (B), 반응성 희석제 (C), 광 중합 개시제 (D) 및 착색제 (E) 를 함유하는 컬러 필터용 감광성 수지 조성물이 제공된다. 용제 (B), 반응성 희석제 (C) 및 광 중합 개시제 (D) 로는, 상기한 것을 사용할 수 있다.In this invention, the photosensitive resin composition for color filters containing a copolymer (A), a solvent (B), a reactive diluent (C), a photoinitiator (D), and a coloring agent (E) is provided. As the solvent (B), the reactive diluent (C), and the photopolymerization initiator (D), those described above can be used.
착색제 (E) 는, 용제 (B) 에 용해 또는 분산되는 것이면 특별히 한정되지 않고, 예를 들어, 염료나 안료 등을 들 수 있다. 염료로는, 용제 (B) 나 알칼리 현상액에 대한 용해성, 감광성 수지 조성물 중의 다른 성분과의 상호 작용, 내열성 등의 관점에서, 카르복실산이나 술폰산 등의 산성기를 갖는 산성 염료, 산성 염료의 질소 화합물과의 염, 산성 염료의 술폰아미드체 등을 사용하는 것이 바람직하다.The colorant (E) is not particularly limited as long as it is dissolved or dispersed in the solvent (B), and examples thereof include dyes and pigments. As the dye, from the viewpoints of solubility in the solvent (B) and alkaline developing solution, interaction with other components in the photosensitive resin composition, heat resistance, etc., acid dyes having acidic groups such as carboxylic acid and sulfonic acid, and nitrogen compounds of acid dyes It is preferable to use a salt with, a sulfonamide form of an acidic dye, and the like.
이와 같은 염료의 예로는, acid alizarin violet N ; acid black 1, 2, 24, 48 ; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147 ; acid chrome violet K ; acid Fuchsin ; acid green 1, 3, 5, 25, 27, 50 ; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95 ; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274 ; acid violet 6B, 7, 9, 17, 19 ; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116 ; food yellow 3 및 이들의 유도체 등을 들 수 있다. 이들 중에서도, 아조계, 크산텐계, 안트라퀴논계 혹은 프탈로시아닌계의 산성 염료가 바람직하다. 이들 염료는, 목적으로 하는 화소의 색에 따라, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다.Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and derivatives thereof; and the like. Among these, acid dyes of azo type, xanthene type, anthraquinone type or phthalocyanine type are preferable. These dyes may be used alone or in combination of two or more, depending on the color of the target pixel.
안료의 예로는, C.I. 피그먼트 옐로우 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 등의 황색 안료 ; C.I. 피그먼트 오렌지 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 등의 등색 안료 ; C.I. 피그먼트 레드 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 등의 적색 안료 ; C.I. 피그먼트 블루 15, 15:3, 15:4, 15:6, 60 등의 청색 안료 ; C.I. 피그먼트 바이올렛 1, 19, 23, 29, 32, 36, 38 등의 바이올렛색 안료 ; C.I. 피그먼트 그린 7, 36, 58, 59 등의 녹색 안료 ; C.I. 피그먼트 브라운 23, 25 등의 갈색 안료 ; C.I. 피그먼트 블랙 1, 7, 카본 블랙, 티탄 블랙, 산화철 등의 흑색 안료 등을 들 수 있다.Examples of pigments include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194, yellow pigments such as 214; C.I. orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 ; C.I. Blue pigments, such as Pigment Blue 15, 15:3, 15:4, 15:6, and 60; C.I. Violet color pigments, such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. Green pigments, such as Pigment Green 7, 36, 58, and 59; C.I. brown pigments such as Pigment Brown 23 and 25; C.I. Black pigments, such as Pigment Black 1 and 7, carbon black, titanium black, and iron oxide, etc. are mentioned.
이들 착색제 (E) 는, 목적으로 하는 화소의 색에 따라, 단독으로 사용해도 되고, 2 종 이상을 조합하여 사용해도 된다. 또한, 목적으로 하는 화소의 색에 따라, 상기의 염료 및 안료를 조합하여 사용할 수도 있다.These coloring agents (E) may be used independently, or may be used in combination of 2 or more types, depending on the color of the target pixel. In addition, it is also possible to use a combination of the above dyes and pigments according to the target color of the pixel.
착색제 (E) 로서 안료를 사용하는 경우, 안료의 분산성을 향상시키는 관점에서, 공지된 분산제를 감광성 수지 조성물에 배합해도 된다. 분산제로는, 시간 경과적인 분산 안정성이 우수한 고분자 분산제를 사용하는 것이 바람직하다. 고분자 분산제의 예로는, 우레탄계 분산제, 폴리에틸렌이민계 분산제, 폴리옥시에틸렌알킬에테르계 분산제, 폴리옥시에틸렌글리콜디에스테르계 분산제, 소르비탄 지방족 에스테르계 분산제, 지방족 변성 에스테르계 분산제 등을 들 수 있다. 이와 같은 고분자 분산제로서, EFKA (에프카 케미컬즈 비브이 (EFKA) 사 제조), Disperbyk (빅케미사 제조), 디스파론 (쿠스모토 화성 주식회사 제조), SOLSPERSE (제네카사 제조) 등의 상품명으로 시판되고 있는 것을 사용해도 된다. 분산제의 배합량은, 사용하는 안료 등의 종류에 따라 적절히 설정하면 된다.When using a pigment as a coloring agent (E), you may mix|blend a well-known dispersing agent with the photosensitive resin composition from a viewpoint of improving the dispersibility of a pigment. As the dispersant, it is preferable to use a polymeric dispersant excellent in dispersion stability over time. Examples of the polymer dispersant include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, aliphatic modified ester-based dispersants, and the like. As such a polymer dispersant, it is marketed under trade names such as EFKA (manufactured by EFKA Chemicals Co., Ltd.), Disperbyk (manufactured by Big Chemie Co., Ltd.), Disparon (manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (manufactured by Zeneca Co., Ltd.). You can use what you have. What is necessary is just to set the compounding quantity of a dispersing agent suitably according to the kind of pigment etc. used.
공중합체 (A), 용제 (B), 반응성 희석제 (C), 광 중합 개시제 (D) 및 착색제 (E) 의 배합량은, 감광성 수지 조성물 중의 공중합체 (A) 와 반응성 희석제 (C) 의 합계량 100 질량부에 대하여, 공중합체 (A) 가 10 ∼ 100 질량부, 용제 (B) 가 30 ∼ 1,000 질량부, 반응성 희석제 (C) 가 0 질량부 초과 ∼ 90 질량부, 광 중합 개시제 (D) 가 0.1 ∼ 30 질량부, 착색제 (E) 가 3 ∼ 80 질량부이고, 바람직하게는, 공중합체 (A) 가 20 ∼ 80 질량부, 용제 (B) 가 50 ∼ 800 질량부, 반응성 희석제 (C) 가 20 ∼ 80 질량부, 광 중합 개시제 (D) 가 0.5 ∼ 20 질량부, 착색제 (E) 가 5 ∼ 70 질량부이고, 보다 바람직하게는, 공중합체 (A) 가 30 ∼ 75 질량부, 용제 (B) 가 100 ∼ 700 질량부, 반응성 희석제 (C) 가 25 ∼ 70 질량부, 광 중합 개시제 (D) 가 1 ∼ 15 질량부, 착색제 (E) 가 10 ∼ 60 질량부이다. 이 범위의 배합량이면, 적절한 점도를 갖는 감광성 수지 조성물이 된다. 또, 착색제 (E) 를 포함하지 않는 감광성 수지 조성물의 경우에도, 공중합체 (A), 용제 (B), 반응성 희석제 (C) 및 광 중합 개시제 (D) 의 배합량은, 상기의 수치 범위가 적용 가능하다.The compounding amounts of the copolymer (A), the solvent (B), the reactive diluent (C), the photopolymerization initiator (D) and the colorant (E) are the total amount of the copolymer (A) and the reactive diluent (C) in the photosensitive resin composition 100 With respect to parts by mass, the copolymer (A) is 10 to 100 parts by mass, the solvent (B) is 30 to 1,000 parts by mass, the reactive diluent (C) is more than 0 to 90 parts by mass, and the photopolymerization initiator (D) is 0.1 to 30 parts by mass, the colorant (E) is 3 to 80 parts by mass, preferably, the copolymer (A) is 20 to 80 parts by mass, the solvent (B) is 50 to 800 parts by mass, the reactive diluent (C) 20 to 80 parts by mass, 0.5 to 20 parts by mass of photopolymerization initiator (D), 5 to 70 parts by mass of colorant (E), more preferably 30 to 75 parts by mass of copolymer (A), solvent (B) is 100-700 mass parts, a reactive diluent (C) is 25-70 mass parts, a photoinitiator (D) is 1-15 mass parts, and a coloring agent (E) is 10-60 mass parts. If it is a compounding quantity within this range, it will become the photosensitive resin composition which has an appropriate viscosity. In addition, even in the case of a photosensitive resin composition containing no colorant (E), the above numerical range applies to the compounding amounts of the copolymer (A), the solvent (B), the reactive diluent (C), and the photopolymerization initiator (D). It is possible.
본 발명의 중합체 조성물 및 감광성 수지 조성물은, 상기의 성분에 더하여, 소정의 특성을 부여하기 위해, 공지된 커플링제, 레벨링제, 열 중합 금지제 등의 공지된 첨가제를 배합해도 된다. 이들 첨가제의 배합량은, 본 발명의 효과를 저해하지 않는 범위이면 특별히 한정되지 않는다.In addition to the components described above, the polymer composition and photosensitive resin composition of the present invention may contain known additives such as a known coupling agent, a leveling agent, and a thermal polymerization inhibitor in order to impart predetermined properties. The blending amount of these additives is not particularly limited as long as it does not impair the effect of the present invention.
본 발명의 감광성 수지 조성물은, 공지된 혼합 장치를 사용하여, 상기의 성분을 혼합함으로써 제조할 수 있다. 또, 원하는 바에 따라, 먼저 공중합체 (A) 및 용제 (B) 를 포함하는 중합체 조성물을 조제한 후, 반응성 희석제 (C), 광 중합 개시제 (D) 및 착색제 (E) 를 혼합하여 제조할 수도 있다.The photosensitive resin composition of this invention can be manufactured by mixing said component using a well-known mixing apparatus. Moreover, if desired, after preparing the polymer composition containing a copolymer (A) and a solvent (B) first, it can also manufacture by mixing a reactive diluent (C), a photoinitiator (D), and a coloring agent (E). .
상기와 같이 하여 얻어지는 감광성 수지 조성물은, 알칼리 현상성을 가지고 있기 때문에, 레지스트로서 바람직한 것이다. 감광성 수지 조성물의 경화는, 베이킹 온도를 250 ℃ 이하의 범위에서 적절히 선택하면 되지만, 본 발명의 공중합체 (A) 는 저온에서의 경화성이 우수하기 때문에, 종래의 재료에 비교하여 베이킹 온도를 낮게 할 수 있다. 감광성 수지 조성물에 있어서 착색제 (E) 로서 안료를 사용한 경우, 베이킹 온도는 160 ℃ 이하에 있어서도 충분한 경화성이 얻어진다. 본 발명의 감광성 수지 조성물은, 베이킹 온도를 낮게 해도 가교 반응이 충분히 진행되기 때문에, 에너지 소비의 면에서 유리하다. 또, 내열성이 열등한 착색제 (E) 나 기판이어도 사용하는 것이 가능해지고, 착색제 본래의 특성이 얻어지거나, 여러 가지 기판에 대한 응용도 가능해진다. 그러한 견지에서, 베이킹 온도는, 210 ℃ 이하로 하는 것이 바람직하고, 보다 바람직하게는 180 ℃ 이하, 가장 바람직하게는 160 ℃ 이하이다. 베이킹 온도의 하한은, 공중합체 (A) 에 포함되는 블록 이소시아나토기의 종류에 따라 반드시 일정하지는 않지만, 그 블록 이소시아나토기의 해리 온도 이상인 것이 필요하고, 통상은 80 ℃ 이상, 바람직하게는 90 ℃ 이상, 보다 바람직하게는 100 ℃ 이상이다. 베이킹 온도가 지나치게 낮아지면, 도막의 내용제성을 충분히 개선하기 어려워진다. 또, 베이킹 시간은 적절히 선택할 수 있지만, 통상은 10 분 ∼ 4 시간, 바람직하게는 20 분 ∼ 2 시간이다.Since the photosensitive resin composition obtained by performing it above has alkali developability, it is suitable as a resist. Curing of the photosensitive resin composition may be performed by appropriately selecting the baking temperature within the range of 250° C. or lower. However, since the copolymer (A) of the present invention has excellent curing properties at low temperatures, the baking temperature can be lowered compared to conventional materials. can When a pigment is used as the coloring agent (E) in the photosensitive resin composition, sufficient curability is obtained even at a baking temperature of 160°C or lower. The photosensitive resin composition of the present invention is advantageous in terms of energy consumption because the crosslinking reaction sufficiently proceeds even at a low baking temperature. In addition, it is possible to use even a colorant (E) or a substrate having poor heat resistance, and the original characteristics of the colorant can be obtained, and application to various substrates is also possible. From that standpoint, the baking temperature is preferably 210°C or lower, more preferably 180°C or lower, and most preferably 160°C or lower. The lower limit of the baking temperature is not necessarily constant depending on the type of block isocyanato group contained in the copolymer (A), but is required to be equal to or higher than the dissociation temperature of the block isocyanato group, and is usually 80°C or higher, preferably. is 90°C or higher, more preferably 100°C or higher. When the baking temperature is too low, it becomes difficult to sufficiently improve the solvent resistance of the coating film. Moreover, although baking time can be selected suitably, it is 10 minutes - 4 hours normally, Preferably they are 20 minutes - 2 hours.
본 발명의 감광성 수지 조성물은, 각종 레지스트, 특히, 유기 EL 디스플레이 (블랙 PDL 용), 액정 표시 장치, CCD 나 CMOS 등의 고체 촬상 소자 등에 삽입되는 컬러 필터를 제조하기 위해 사용되는 레지스트로서 바람직하다. 또, 본 발명의 감광성 수지 조성물은, 내용제성, 저온에서의 경화 특성 등이 우수한 경화 도막을 부여하기 때문에, 각종 코팅, 접착제, 인쇄 잉크용 바인더 등에 사용할 수도 있다.The photosensitive resin composition of the present invention is suitable as a resist used for producing various resists, particularly color filters incorporated in organic EL displays (for black PDLs), liquid crystal display devices, solid-state imaging devices such as CCD and CMOS. In addition, since the photosensitive resin composition of the present invention gives a cured coating film excellent in solvent resistance, curing properties at low temperatures, etc., it can also be used for various coatings, adhesives, binders for printing inks, and the like.
본 발명의 감광성 수지 조성물은, 현상성 및 보존 안정성이 양호함과 함께, 패턴 형성시의 베이킹 온도를 낮게 해도 내용제성이 우수한 착색 패턴을 형성할 수 있기 때문에, 컬러 필터용의 감광성 재료로서 매우 유용하다. 또, 본 발명의 감광성 수지 조성물은, 저온 경화에 수반하여 플렉시블 디스플레이의 발전, 제조 공정에 있어서의 에너지 소비의 저감, 그리고, 사용하는 착색제의 제한 완화에 대해서도 공헌할 수 있다.The photosensitive resin composition of the present invention is very useful as a photosensitive material for color filters because it has good developability and storage stability and can form a colored pattern having excellent solvent resistance even when the baking temperature at the time of pattern formation is low. Do. Moreover, the photosensitive resin composition of this invention can contribute also to the development of a flexible display accompanying low-temperature hardening, the reduction of energy consumption in a manufacturing process, and relaxation of restrictions of the colorant to be used.
<컬러 필터><Color filter>
다음으로, 본 발명의 감광성 수지 조성물의 경화물로 이루어지는 착색 패턴을 갖는 컬러 필터에 대하여 설명한다. 본 발명의 컬러 필터는, 상기의 감광성 수지 조성물을 사용하여 형성되는 착색 패턴을 갖는다. 컬러 필터는, 통상, 기판과, 그 위에 형성되는 RGB 의 화소, 각각의 화소의 경계에 형성되는 블랙 매트릭스 및 화소와 블랙 매트릭스 상에 형성되는 보호막으로 구성된다. 이 구성에 있어서, 화소 및 블랙 매트릭스 (착색 패턴) 가 상기의 감광성 수지 조성물을 사용하여 형성되는 것을 제외하면, 그 밖의 구성은 공지된 것을 채용할 수 있다.Next, a color filter having a color pattern made of a cured product of the photosensitive resin composition of the present invention will be described. The color filter of the present invention has a color pattern formed using the photosensitive resin composition described above. The color filter is usually composed of a substrate, RGB pixels formed thereon, a black matrix formed at the boundary between the respective pixels, and a protective film formed on the pixels and the black matrix. In this structure, except that the pixels and the black matrix (coloring pattern) are formed using the above photosensitive resin composition, other structures can employ known ones.
다음으로, 컬러 필터의 제조 방법의 일 실시형태에 대하여 설명한다. 먼저, 기판 상에 착색 패턴을 형성한다. 구체적으로는, 기판 상에, 블랙 매트릭스 및 RGB 의 화소를 순차 형성한다. 기판의 재질은, 특별히 한정되는 것은 아니고, 유리 기판, 실리콘 기판, 폴리카보네이트 기판, 폴리에스테르 기판, 폴리아미드 기판, 폴리아미드이미드 기판, 폴리이미드 기판, 알루미늄 기판, 프린트 배선 기판, 어레이 기판 등을 적절히 사용할 수 있다.Next, an embodiment of a method for manufacturing a color filter will be described. First, a coloring pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on a substrate. The material of the substrate is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, an array substrate, etc. are appropriately selected. can be used
착색 패턴은, 포토리소그래피법에 의해 형성할 수 있다. 구체적으로는, 상기의 감광성 수지 조성물을 기판 상에 도포하여 도포막을 형성한 후, 소정 패턴의 포토마스크를 개재하여 도포막을 노광하고 노광 부분을 광 경화시킨다. 그리고, 미노광 부분을 알칼리 수용액으로 현상한 후, 베이킹함으로써, 소정의 착색 패턴을 형성할 수 있다.A coloring pattern can be formed by a photolithography method. Specifically, after applying the above photosensitive resin composition on a substrate to form a coating film, the coating film is exposed to light through a photomask having a predetermined pattern, and the exposed portion is photocured. And after developing an unexposed part with aqueous alkali solution, a predetermined|prescribed coloring pattern can be formed by baking.
감광성 수지 조성물의 도포 방법으로는, 특별히 한정되지 않지만, 스크린 인쇄법, 롤 코트법, 커튼 코트법, 스프레이 코트법, 스핀 코트법 등을 사용할 수 있다. 또, 감광성 수지 조성물의 도포 후, 필요에 따라, 순환식 오븐, 적외선 히터, 핫 플레이트 등의 가열 수단을 사용하여 가열함으로써 용제 (B) 를 휘발시켜도 된다. 가열 조건은, 특별히 한정되지 않고, 사용하는 감광성 수지 조성물의 종류에 따라 적절히 설정하면 된다. 일반적으로는, 50 ℃ ∼ 120 ℃ 의 온도에서 30 초 ∼ 30 분 가열하면 된다.Although it does not specifically limit as a method of applying the photosensitive resin composition, A screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, etc. can be used. Moreover, you may volatilize the solvent (B) by heating using heating means, such as a circulation type oven, an infrared heater, and a hot plate, after application|coating of the photosensitive resin composition as needed. Heating conditions are not specifically limited, What is necessary is just to set suitably according to the kind of photosensitive resin composition to be used. Generally, what is necessary is just to heat at the temperature of 50 degreeC - 120 degreeC for 30 second - 30 minutes.
이어서, 형성된 도막에 네거티브형의 마스크를 개재하여 자외선, 엑시머 레이저광 등의 활성 에너지선을 조사하여 부분적으로 노광한다. 조사하는 에너지선량은, 감광성 수지 조성물의 조성에 따라 적절히 선택하면 되고, 예를 들어, 30 ∼ 2000 mJ/㎠ 인 것이 바람직하다. 노광에 사용되는 광원으로는, 특별히 한정되지 않지만, 저압 수은 램프, 중압 수은 램프, 고압 수은 램프, 크세논 램프, 메탈 할라이드 램프 등을 사용할 수 있다.Subsequently, active energy rays such as ultraviolet rays and excimer laser light are irradiated to the formed coating film through a negative mask to partially expose it. The amount of energy radiation to be irradiated may be appropriately selected according to the composition of the photosensitive resin composition, and is preferably 30 to 2000 mJ/cm 2 , for example. The light source used for exposure is not particularly limited, but a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used.
현상에 사용되는 알칼리 수용액으로는, 특별히 한정되지 않지만, 탄산나트륨, 탄산칼륨, 탄산칼슘, 수산화나트륨, 수산화칼륨 등의 수용액 ; 에틸아민, 디에틸아민, 디메틸에탄올아민 등의 아민계 화합물의 수용액 ; 테트라메틸암모늄, 3-메틸-4-아미노-N,N-디에틸아닐린, 3-메틸-4-아미노-N-에틸-N-β-하이드록시에틸아닐린, 3-메틸-4-아미노-N-에틸-N-β-메탄술폰아미드에틸아닐린, 3-메틸-4-아미노-N-에틸-N-β-메톡시에틸아닐린 및 이들의 황산염, 염산염 또는 p-톨루엔술폰산염 등의 p-페닐렌디아민계 화합물의 수용액 등을 사용할 수 있다. 또한, 이들 수용액에는, 필요에 따라 소포제나 계면 활성제를 첨가해도 된다. 또, 상기의 알칼리 수용액에 의한 현상 후, 수세하고 건조시키는 것이 바람직하다.Although it does not specifically limit as aqueous alkali solution used for image development, Aqueous solutions, such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; Tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N -Ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and p-phenyl such as sulfates, hydrochlorides or p-toluenesulfonates thereof An aqueous solution of a rendiamine-based compound or the like can be used. Moreover, you may add an antifoamer and surfactant to these aqueous solutions as needed. Moreover, it is preferable to wash with water and dry after image development by said aqueous alkali solution.
베이킹의 조건은, 특별히 한정되지 않고, 사용하는 감광성 수지 조성물의 종류에 따라 가열 처리를 실시하면 된다. 종래의 감광성 수지 조성물에서는, 베이킹 온도가 200 ℃ 이하가 되면 착색 패턴의 내용제성이 부족하지만, 본 발명의 감광성 수지 조성물에서는, 120 ℃ 이하의 온도에서 베이킹한 경우라도 충분한 내용제성을 나타내는 착색 패턴을 형성할 수 있다. 그 때문에, 베이킹 온도를 낮게 할 수 있고, 또, 고온에서 베이킹하는 경우에는 처리 시간을 단축할 수 있어, 제조상의 큰 이점이 된다. 이와 같은 견지에서, 베이킹 온도를, 통상은 210 ℃ 이하, 바람직하게는 160 ℃ 이하, 보다 바람직하게는 120 ℃ 이하로 하고, 베이킹 시간을, 통상은 10 분 ∼ 4 시간, 바람직하게는 20 분 ∼ 2 시간으로 하여 실시된다.The conditions of baking are not specifically limited, What is necessary is just to heat-process according to the kind of photosensitive resin composition to be used. In the conventional photosensitive resin composition, the solvent resistance of the colored pattern is insufficient when the baking temperature is 200 ° C. or less, but in the photosensitive resin composition of the present invention, the colored pattern showing sufficient solvent resistance even when baking at a temperature of 120 ° C. or less can form Therefore, the baking temperature can be lowered and, in the case of baking at a high temperature, the processing time can be shortened, which is a great advantage in terms of manufacturing. From such a standpoint, the baking temperature is usually 210 ° C. or less, preferably 160 ° C. or less, more preferably 120 ° C. or less, and the baking time is usually 10 minutes to 4 hours, preferably 20 minutes to It is carried out for 2 hours.
상기와 같은 도포, 노광, 현상 및 베이킹을, 블랙 매트릭스용의 감광성 수지 조성물, 및 적색, 녹색, 청색의 화소용 감광성 수지 조성물을 사용하여 순차 반복함으로써, 원하는 착색 패턴을 형성할 수 있다. 또한, 상기에서는, 광 경화에 의한 착색 패턴의 형성 방법을 설명했지만, 광 중합 개시제 (D) 대신에, 경화 촉진제 및 공지된 에폭시 수지를 배합한 감광성 수지 조성물을 사용하면, 잉크젯법에 의해 도포한 후, 가열함으로써, 원하는 착색 패턴을 형성할 수도 있다. 다음으로, 착색 패턴 (RGB 의 각 화소 및 블랙 매트릭스) 상에 보호막을 형성한다. 보호막으로는, 특별히 한정되지 않고, 공지된 것을 사용하여 형성하면 된다.A desired coloring pattern can be formed by sequentially repeating the above coating, exposure, development, and baking using the photosensitive resin composition for black matrix and the photosensitive resin composition for red, green, and blue pixels. In addition, although the formation method of the coloring pattern by photocuring was explained above, if the photosensitive resin composition which mix|blended the hardening accelerator and a well-known epoxy resin was used instead of the photoinitiator (D), it applied by the inkjet method Then, by heating, a desired coloring pattern can also be formed. Next, a protective film is formed on the color pattern (each pixel of RGB and the black matrix). It does not specifically limit as a protective film, What is necessary is just to form using a well-known thing.
이와 같이 하여 제조되는 컬러 필터는, 감도나 현상성이 우수함과 함께, 저온에서의 경화가 가능하고 내용제성이 우수한 착색 패턴을 부여하는 감광성 수지 조성물을 사용하여 제조하고 있기 때문에, 색변화가 적은 우수한 착색 패턴을 갖는다.Since the color filter produced in this way is produced using a photosensitive resin composition that is excellent in sensitivity and developability, can be cured at low temperatures and provides a coloring pattern with excellent solvent resistance, it has excellent color change with little color change. It has a color pattern.
<화상 표시 소자><Image display element>
본 발명의 화상 표시 소자는, 상기의 컬러 필터를 구비한 화상 표시 소자이고, 그 구체예로서, 액정 표시 소자, 유기 EL 표시 소자, CCD 소자나 CMOS 소자 등의 고체 촬상 소자 등을 들 수 있다. 본 발명의 화상 표시 소자의 제조는, 상기의 컬러 필터를 사용하는 것 이외에, 통상적인 방법에 따라 실시하면 된다. 예를 들어, 액정 표시 소자를 제조하는 경우에는, 기판 상에, 상기 컬러 필터를 형성하고, 이어서, 전극, 스페이서 등을 순차 형성한다. 그리고, 또 다른 한 장의 기판 상에 전극 등을 형성하고, 양자를 첩합하고 소정량의 액정을 주입, 봉지하면 된다.The image display element of the present invention is an image display element provided with the above color filter, and specific examples thereof include solid-state imaging elements such as liquid crystal display elements, organic EL display elements, CCD elements and CMOS elements. What is necessary is just to manufacture the image display element of this invention in accordance with a conventional method other than using the said color filter. For example, when manufacturing a liquid crystal display element, the said color filter is formed on a board|substrate, and then electrodes, a spacer, etc. are formed one by one. Then, an electrode or the like is formed on another substrate, and the two are bonded together, and a predetermined amount of liquid crystal is injected and sealed.
실시예Example
이하, 실시예를 참조하여 본 발명을 상세히 설명하지만, 본 발명은 이들 실시예에 의해 한정되지 않는다. 또한, 이 실시예에 있어서, 부 및 퍼센트라고 되어 있는 것은 특별히 언급하지 않는 한, 모두 질량 기준이다. 또, 산가, 중량 평균 분자량의 측정법은 이하와 같다.Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by these examples. Incidentally, in this embodiment, parts and percentages are all based on mass unless otherwise specified. Moreover, the measuring method of an acid value and a weight average molecular weight is as follows.
(1) 산가 : JIS K6901 5.3 에 따라서 측정된 공중합체 (A) 의 산가로서, 그 공중합체 (A) 1 g 중에 포함되는 산성 성분을 중화하는 데 필요로 하는 수산화칼륨의 mg 수를 의미한다.(1) Acid value: The acid value of the copolymer (A) measured according to JIS K6901 5.3, which means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the copolymer (A).
(2) 중량 평균 분자량 (Mw) 이란, 겔 퍼미에이션 크로마토그래피 (GPC) 를 사용하여, 하기 조건에서 측정한 표준 폴리스티렌 환산 중량 평균 분자량을 의미한다.(2) The weight average molecular weight (Mw) means the standard polystyrene equivalent weight average molecular weight measured under the following conditions using gel permeation chromatography (GPC).
칼럼 : 쇼덱스 (등록상표) LF-804+LF-804 (쇼와 전공 주식회사 제조)Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.)
칼럼 온도 : 40 ℃Column temperature: 40 ℃
시료 : 공중합체의 0.2 % 테트라하이드로푸란 용액Sample: 0.2% tetrahydrofuran solution of the copolymer
전개 용매 : 테트라하이드로푸란Developing solvent: tetrahydrofuran
검출기 : 시차 굴절계 (쇼덱스 RI-71S) (쇼와 전공 주식회사 제조)Detector: Differential refractometer (Shodex RI-71S) (manufactured by Showa Denko Co., Ltd.)
유속 : 1 ㎖/분Flow rate: 1 ml/min
[실시예 1][Example 1]
교반 장치, 적하 깔때기, 콘덴서, 온도계 및 가스 도입관을 구비한 플라스크에, 257.3 g 의 디에틸렌글리콜메틸에틸에테르를 넣은 후, 질소 치환하면서 교반하고, 78 ℃ 로 승온하였다. 다음으로, 110.0 g 의 디시클로펜타닐메타크릴레이트, 17.0 g 의 글리시딜메타크릴레이트, 28.4 g 의 메타크릴산 및 12.1 g 의 메타크릴산2-[O-(1'-메틸프로필리덴아미노)카르복시아미노]에틸 (카렌즈 MOI-BM, 쇼와 전공 주식회사 제조, 블록 이소시아나토기의 해리율 : 18 질량%) 로 이루어지는 단량체 혼합물과, 13.4 g 의 2,2'-아조비스(2,4-디메틸발레로니트릴) (중합 개시제) 을 78.7 g 의 디에틸렌글리콜메틸에틸에테르에 첨가하고 용해시킨 것을 각각 적하 깔때기로부터 플라스크 중에 적하하였다. 적하 종료 후, 78 ℃ 에서 3 시간 교반하여 공중합 반응을 실시하고, 공중합체를 생성시켜, 시료 No.1 의 중합체 조성물 (용제 이외의 성분 농도 40 질량%) 을 얻었다. 얻어진 중합체 조성물 중의 공중합체의 중량 평균 분자량은 7,500 이고, 산가는 102.3 KOHmg/g 이었다.After putting 257.3 g of diethylene glycol methyl ethyl ether in a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube, the mixture was stirred while purging with nitrogen, and the temperature was raised to 78°C. Next, 110.0 g of dicyclopentanyl methacrylate, 17.0 g of glycidyl methacrylate, 28.4 g of methacrylic acid and 12.1 g of methacrylic acid 2-[O-(1'-methylpropylideneamino) Carboxyamino] ethyl (Karenz MOI-BM, manufactured by Showa Electric Co., Ltd., dissociation rate of block isocyanato group: 18% by mass) and a monomer mixture consisting of 13.4 g of 2,2'-azobis (2,4 -Dimethylvaleronitrile) (polymerization initiator) was added and dissolved in 78.7 g of diethylene glycol methyl ethyl ether and each was added dropwise into the flask from the dropping funnel. After completion of the dropwise addition, a copolymerization reaction was carried out by stirring at 78°C for 3 hours to form a copolymer to obtain a polymer composition of Sample No. 1 (concentration of components other than the solvent: 40% by mass). The weight average molecular weight of the copolymer in the obtained polymer composition was 7,500, and the acid value was 102.3 KOHmg/g.
[실시예 2 ∼ 12 및 비교예 1 ∼ 3][Examples 2 to 12 and Comparative Examples 1 to 3]
표 1 및 2 에 기재된 원료를 사용하는 것 이외에는 실시예 1 과 동일한 조건에서 공중합 반응을 실시하여, 시료 No.2 ∼ 15 의 중합체 조성물 (용제 이외의 성분 농도 40 질량%) 을 얻었다. 얻어진 중합체 조성물 중의 공중합체의 중량 평균 분자량 및 산가를 표 1 및 2 에 나타낸다. 또한, 표 1 및 2 에 있어서, 메타크릴산2-(3,5-디메틸피라졸-1-일)카르보닐아미노에틸은, 쇼와 전공 주식회사 제조, 카렌즈 MOI-BP, 블록 이소시아나토기의 해리율 : 70 질량% 이고, 말론산-2-[[[2-메틸-1-옥소-2-프로페닐]옥시]에틸]아미노]카르보닐]-1,3디에틸에스테르는, 쇼와 전공 주식회사 제조, 카렌즈 MOI-DEM, 블록 이소시아나토기의 해리율 : 90 질량% 이고, 벤조산-4-[[[[2-[(2-메틸-1-옥소-2-프로펜-1-일)옥시]에틸]아민]카르보닐]옥시]메틸에스테르는, 블록 이소시아나토기의 해리율 : 40 질량% 이고, 벤조산-2-[[[[2-[(2-메틸-1-옥시-2-프로펜-1-일)옥시]에틸]아민]카르보닐]옥시]메틸에스테르는, 블록 이소시아나토기의 해리율 : 75 질량% 이고, 2-프로펜산-2-메틸-2-[[(3,5-디메틸페녹시)카르보닐]아민]에틸에스테르는, 블록 이소시아나토기의 해리율 : 28 질량% 이다.Except for using the raw materials described in Tables 1 and 2, a copolymerization reaction was carried out under the same conditions as in Example 1 to obtain polymer compositions of Sample Nos. 2 to 15 (concentration of components other than the solvent: 40% by mass). The weight average molecular weight and acid value of the copolymer in the obtained polymer composition are shown in Tables 1 and 2. In Tables 1 and 2, 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate is Showa Electric Co., Ltd., Karenz MOI-BP, block isocyanato group Dissociation rate: 70% by mass, and malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester is Showa Manufactured by Denko Corporation, Karenz MOI-DEM, block isocyanato group dissociation rate: 90% by mass, benzoic acid-4-[[[[2-[(2-methyl-1-oxo-2-propene-1 -yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester has a block isocyanato group dissociation rate of 40% by mass, and is benzoic acid-2-[[[[2-[(2-methyl-1- Oxy-2-propen-1-yl) oxy] ethyl] amine] carbonyl] oxy] methyl ester has a block isocyanato group dissociation rate: 75% by mass, and 2-propenoic acid-2-methyl-2 -[[(3,5-dimethylphenoxy)carbonyl]amine] ethyl ester has a block isocyanato group dissociation rate: 28% by mass.
[실시예 13 ∼ 24 및 비교예 4 ∼ 6][Examples 13 to 24 and Comparative Examples 4 to 6]
<감광성 수지 조성물 (안료 타입) 의 조제><Preparation of photosensitive resin composition (pigment type)>
직경 0.5 ㎜ 의 지르코니아 비즈 200 질량부를 충전한 스테인리스제 용기에, C.I 피그먼트 그린 36 (착색제) 을 100 질량부, 프로필렌글리콜모노메틸에테르아세테이트를 44.98 질량부, 분산제 (빅케미·재팬 주식회사 제조 Disperbyk-161) 를 25 질량부 투입하고, 페인트 셰이커로 2 시간 혼합하여 분산시킴으로써, 녹색 안료 분산액을 조제하였다.In a stainless steel container filled with 200 parts by mass of zirconia beads having a diameter of 0.5 mm, 100 parts by mass of C.I. Pigment Green 36 (colorant), 44.98 parts by mass of propylene glycol monomethyl ether acetate, and a dispersing agent (Disperbyk- by Big Chemie Japan Co., Ltd.) 161) was added in 25 parts by mass, and mixed and dispersed in a paint shaker for 2 hours to prepare a green pigment dispersion.
이 녹색 안료 분산액을, 표 3 에 나타내는 그 밖의 배합 성분 (즉, 중합체 조성물, 반응성 희석제, 광 중합 개시제 및 용제) 과 혼합하여 감광성 수지 조성물을 조제하였다. 각각의 성분의 배합량은, 표 3 에 나타내는 바와 같다. 또한, 실시예 13 ∼ 24 의 감광성 수지 조성물은, 실시예 1 ∼ 12 (시료 No.1 ∼ 12) 의 중합체 조성물 각각을 사용하여 조제하고, 비교예 4 ∼ 6 의 감광성 수지 조성물은, 비교예 1 ∼ 3 (시료 No.13 ∼ 15) 의 중합체 조성물 각각을 사용하여 조제하였다. 또, 중합체 조성물의 양은 공중합체 반응 종료시에 포함되는 용제를 포함하고, 각 시료에 포함되는 용제의 양도, 배합 성분으로서의 용제 중에 합산되어 있다.The photosensitive resin composition was prepared by mixing this green pigment dispersion with other compounding components shown in Table 3 (ie, polymer composition, reactive diluent, photopolymerization initiator and solvent). The blending amount of each component is as shown in Table 3. In addition, the photosensitive resin compositions of Examples 13 to 24 were prepared using each of the polymer compositions of Examples 1 to 12 (Sample Nos. 1 to 12), and the photosensitive resin compositions of Comparative Examples 4 to 6 were prepared using Comparative Example 1 It prepared using each of the polymer compositions of -3 (sample No. 13-15). In addition, the amount of the polymer composition includes the solvent contained at the end of the copolymer reaction, and the amount of the solvent contained in each sample is added to the solvent as a compounding component.
<감광성 수지 조성물의 평가><Evaluation of photosensitive resin composition>
(1) 알칼리 현상성(1) alkali developability
실시예 13 ∼ 24 및 비교예 4 ∼ 6 의 감광성 수지 조성물 각각을, 가로세로 5 ㎝ 의 유리 기판 (무알칼리 유리 기판) 상에, 노광 후의 두께가 2.5 ㎛ 가 되도록 스핀 코트한 후, 90 ℃ 에서 3 분간 가열함으로써 용제를 휘발시켰다. 다음으로, 도포막으로부터 100 ㎛ 의 거리에 소정 패턴의 포토마스크를 배치하고, 이 포토마스크를 개재하여 도포막을 노광 (노광량 : 150 mJ/㎠) 하고, 노광 부분을 광 경화시켰다. 다음으로, 0.1 질량% 의 탄산나트륨을 포함하는 수용액을 23 ℃ 의 온도 및 0.3 ㎫ 의 압력으로 스프레이함으로써 미노광 부분을 용해시켜 현상한 후, 100 ℃ 에서 20 분간 베이킹함으로써 소정의 패턴을 형성하였다. 알칼리 현상 후의 잔류물은, 알칼리 현상 후의 패턴을, (주) 히타치 하이테크놀로지즈 제조의 전자 현미경 S-3400 을 사용하여 관찰함으로써 확인하였다. 이 평가의 기준은 이하와 같다.After spin-coating each of the photosensitive resin compositions of Examples 13 to 24 and Comparative Examples 4 to 6 on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness after exposure is 2.5 μm, at 90 ° C. The solvent was volatilized by heating for 3 minutes. Next, a photomask of a predetermined pattern was arranged at a distance of 100 μm from the coating film, the coating film was exposed through the photomask (exposure amount: 150 mJ/cm 2 ), and the exposed portion was photocured. Next, after spraying an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23°C and a pressure of 0.3 MPa to dissolve the unexposed portion and developing, a predetermined pattern was formed by baking at 100°C for 20 minutes. The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi High-Technologies Co., Ltd. The criteria for this evaluation are as follows.
○ : 잔류물 없음○: no residue
× : 잔류물 있음×: with residue
알칼리 현상성의 평가 결과를 표 4 에 나타낸다.The evaluation results of alkali developability are shown in Table 4.
(2) 내용제성의 평가(2) Evaluation of solvent resistance
가로세로 5 ㎝ 의 유리 기판 (무알칼리 유리 기판) 상에, 실시예 13 ∼ 24 및 비교예 4 ∼ 6 의 감광성 수지 조성물 각각을, 베이킹 후의 두께가 2.5 ㎛ 가 되도록 스핀 코트한 후, 90 ℃ 에서 3 분간 가열하여 용제를 휘발시켰다. 다음으로, 도포막에 파장 365 ㎚ 의 광을 노광하고, 노광 부분을 광 경화시킨 후, 베이킹 온도 100 ℃ 의 건조기 중에 20 분간 방치하여 경화 도막을 제작하였다. 용량 500 ㎖ 의 뚜껑 부착 유리병에 200 ㎖ 의 프로필렌글리콜모노메틸에테르아세테이트를 넣고, 80 ℃ 의 조건하에 정치하였다. 그 속에 상기의 경화 도막 부착 시험편을 침지한 후, 80 ℃ 로 유지한 상태에서, 5 분 정치하였다. 시험편을 프로필렌글리콜모노메틸에테르아세테이트에 침지시키기 전후의 색변화 (ΔE*ab) 를 분광 광도계 UV-1650PC (주식회사 시마즈 제작소 제조) 로 측정하였다. ΔE*ab 의 측정 결과를 표 4 에 나타낸다. ΔE*ab 가 1.5 이하이면 내용제성이 우수하다고 할 수 있다.On a 5 cm square glass substrate (alkali-free glass substrate), each of the photosensitive resin compositions of Examples 13 to 24 and Comparative Examples 4 to 6 was spin-coated so that the thickness after baking was 2.5 μm, and then at 90 ° C. The solvent was volatilized by heating for 3 minutes. Next, after exposing the coating film to light with a wavelength of 365 nm and photocuring the exposed portion, it was left to stand for 20 minutes in a dryer with a baking temperature of 100°C to produce a cured coating film. 200 ml of propylene glycol monomethyl ether acetate was placed in a 500 ml capped glass bottle, and the mixture was allowed to stand still at 80°C. After immersing the said test piece with a cured coating film in it, it was left still for 5 minutes in the state maintained at 80 degreeC. The color change (ΔE*ab) before and after immersing the test piece in propylene glycol monomethyl ether acetate was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). The measurement results of ΔE*ab are shown in Table 4. When ΔE*ab is 1.5 or less, it can be said that the solvent resistance is excellent.
(3) 보존 안정성의 평가(3) Evaluation of storage stability
실시예 1 ∼ 12 및 비교예 1 ∼ 3 의 공중합체를, 유리 용기에 등량씩 칭량하여 넣고, 먼지 등이 들어가지 않도록 알루미늄박으로 입구를 닫았다. 다음으로, 이들 샘플을 각각 23 ℃ 로 유지한 항온기 중에 정치하고, 샘플의 1 개월 후의 중량 평균 분자량 (Mw) 을 측정하였다. 1 개월 후의 Mw 의 변화율을 표 5 에 나타낸다. 1 개월 후의 Mw 의 변화율이 20 % 이내이면, 공중합체의 보존 안정성이 우수하다고 할 수 있다.Equal amounts of the copolymers of Examples 1 to 12 and Comparative Examples 1 to 3 were weighed and put into a glass container, and the inlet was closed with an aluminum foil to prevent dust or the like from entering. Next, each of these samples was left still in an incubator maintained at 23°C, and the weight average molecular weight (Mw) of the sample after one month was measured. Table 5 shows the change rate of Mw after one month. If the change rate of Mw after one month is within 20%, it can be said that the copolymer has excellent storage stability.
표 4 의 결과로부터 알 수 있는 바와 같이, 시료 No.1 ∼ 12 의 중합체 조성물을 사용한 실시예 13 ∼ 24 의 감광성 수지 조성물은, 알칼리 현상성 및 내용제성이 양호하였다. 또한, 공중합체의 보존 안정성은, 그것을 배합한 감광성 수지 조성물의 보존 안정성과 상관이 있기 때문에, 표 5 의 결과로부터, 시료 No.1 ∼ 12 의 중합체 조성물을 사용한 실시예 13 ∼ 24 의 감광성 수지 조성물은 보존 안정성도 양호하다고 할 수 있다. 이에 대하여, 시료 No.13 ∼ 15 의 중합체 조성물을 사용한 비교예 4 ∼ 6 의 감광성 수지 조성물은, 보존 안정성이 양호하기는 하지만, 내용제성이 충분하지 않고, 또, 비교예 6 의 감광성 수지 조성물은, 알칼리 현상성도 충분하지 않았다.As can be seen from the results of Table 4, the photosensitive resin compositions of Examples 13 to 24 using the polymer compositions of Sample Nos. 1 to 12 had good alkali developability and solvent resistance. In addition, since the storage stability of the copolymer correlates with the storage stability of the photosensitive resin composition blended with it, from the results of Table 5, the photosensitive resin compositions of Examples 13 to 24 using the polymer compositions of Sample Nos. 1 to 12 It can be said that the storage stability is also good. In contrast, the photosensitive resin compositions of Comparative Examples 4 to 6 using the polymer compositions of Sample Nos. 13 to 15 have good storage stability, but do not have sufficient solvent resistance, and the photosensitive resin compositions of Comparative Example 6 , alkali developability was also not sufficient.
이상의 결과로부터 알 수 있는 바와 같이, 본 발명에 의하면, 현상성이 양호함과 함께, 내용제성 및 보존 안정성이 우수한 감광성 수지 조성물을 제공할 수 있다. 또, 본 발명에 의하면, 상기와 같은 특성을 갖는 감광성 수지 조성물의 조제에 유용한 공중합체를 제공할 수 있다.As can be seen from the above results, according to the present invention, a photosensitive resin composition having excellent developability and excellent solvent resistance and storage stability can be provided. Moreover, according to this invention, the copolymer useful for preparation of the photosensitive resin composition which has the above characteristics can be provided.
또한, 본 국제 출원은, 2017년 8월 3일에 출원한 일본 특허출원 제2017-150501호에 기초하는 우선권을 주장하는 것이고, 이 일본 특허출원의 전체 내용을 본 국제 출원에 원용한다.In addition, this international application claims priority based on Japanese Patent Application No. 2017-150501 for which it applied on August 3, 2017, and uses all the content of this Japanese patent application for this international application.
Claims (19)
상기 공중합체 (A) 가, 블록 이소시아나토기를 갖는 구성 단위 (a), 산기를 갖는 구성 단위 (b) 및 에폭시기를 갖는 구성 단위 (c) 를 함유하고,
상기 블록 이소시아나토기를 갖는 구성 단위 (a) 가, 메타크릴산2-(3,5-디메틸피라졸-1-일)카르보닐아미노에틸, 메타크릴산2-[O-(1'-메틸프로필리덴아미노)카르복시아미노]에틸, 말론산-2-[[[2-메틸-1-옥소-2-프로페닐]옥시]에틸]아미노]카르보닐]-1,3디에틸에스테르, 벤조산-4-[[[[2-[(2-메틸-1-옥소-2-프로펜-1-일)옥시]에틸]아미노]카르보닐]옥시]메틸에스테르, 벤조산-2-[[[[2-[(2-메틸-1-옥시-2-프로펜-1-일)옥시]에틸]아미노]카르보닐]옥시]메틸에스테르 및 2-프로펜산-2-메틸-2-[[(3,5-디메틸페녹시)카르보닐]아미노]에틸에스테르로 이루어지는 군에서 선택되는 적어도 1 종 유래의 구성 단위이고,
산가가 20 ∼ 300 KOHmg/g 인 것을 특징으로 하는 감광성 수지 조성물.containing a copolymer (A), a solvent (B), a reactive diluent (C) and a photopolymerization initiator (D);
The copolymer (A) contains a structural unit (a) having a block isocyanato group, a structural unit (b) having an acid group, and a structural unit (c) having an epoxy group,
Structural unit (a) having the block isocyanato group is methacrylic acid 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl, methacrylic acid 2-[O-(1'-) Methylpropylideneamino)carboxyamino]ethyl, malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, benzoic acid- 4-[[[[2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2 -[(2-methyl-1-oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester and 2-propenoic acid-2-methyl-2-[[(3, 5-dimethylphenoxy) carbonyl] amino] a structural unit derived from at least one member selected from the group consisting of ethyl esters;
A photosensitive resin composition having an acid value of 20 to 300 KOHmg/g.
상기 공중합체 (A) 가, 상기 블록 이소시아나토기를 갖는 구성 단위 (a) 를 1 ∼ 60 몰%, 상기 산기를 갖는 구성 단위 (b) 를 5 ∼ 65 몰% 및 상기 에폭시기를 갖는 구성 단위 (c) 를 5 ∼ 65 몰% 함유하는 감광성 수지 조성물.According to claim 1,
The copolymer (A) contains 1 to 60 mol% of the structural unit (a) having the block isocyanato group, and 5 to 65 mol% of the structural unit (b) having the acid group and the structural unit having the epoxy group The photosensitive resin composition containing 5-65 mol% of (c).
상기 공중합체 (A) 에 있어서의 상기 블록 이소시아나토기를 갖는 구성 단위 (a) 와 상기 에폭시기를 갖는 구성 단위 (c) 의 몰비율이, 10 : 90 ∼ 75 : 25 인 감광성 수지 조성물.According to claim 1,
The photosensitive resin composition whose molar ratio of the structural unit (a) which has the said block isocyanato group in the said copolymer (A), and the structural unit (c) which has the said epoxy group is 10:90 - 75:25.
상기 공중합체 (A) 가, 메타크릴산2-(3,5-디메틸피라졸-1-일)카르보닐아미노에틸, 메타크릴산2-[O-(1'-메틸프로필리덴아미노)카르복시아미노]에틸, 말론산-2-[[[2-메틸-1-옥소-2-프로페닐]옥시]에틸]아미노]카르보닐]-1,3디에틸에스테르, 벤조산-4-[[[[2-[(2-메틸-1-옥소-2-프로펜-1-일)옥시]에틸]아미노]카르보닐]옥시]메틸에스테르, 벤조산-2-[[[[2-[(2-메틸-1-옥시-2-프로펜-1-일)옥시]에틸]아미노]카르보닐]옥시]메틸에스테르 및 2-프로펜산-2-메틸-2-[[(3,5-디메틸페녹시)카르보닐]아미노]에틸에스테르로 이루어지는 군에서 선택되는 적어도 1 종 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜메타크릴레이트 유래의 구성 단위 (c) 와, 디시클로펜타닐메타크릴레이트 및 메틸(메트)아크릴레이트로 이루어지는 군에서 선택되는 적어도 1 종 유래의 구성 단위 (e) 를 함유하는 감광성 수지 조성물.According to claim 1,
The copolymer (A) is methacrylic acid 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl, methacrylic acid 2-[O-(1'-methylpropylideneamino)carboxyamino ]ethyl, malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, benzoic acid-4-[[[[2 -[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2-methyl- 1-oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methylester and 2-propenoic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carb A structural unit (a) derived from at least one selected from the group consisting of [bornyl] amino] ethyl ester, a structural unit (b) derived from (meth)acrylic acid, and a structural unit (c) derived from glycidyl methacrylate and a structural unit (e) derived from at least one member selected from the group consisting of dicyclopentanyl methacrylate and methyl (meth)acrylate.
상기 공중합체 (A) 가, 수산기를 갖는 구성 단위 (d) 를 추가로 함유하는 감광성 수지 조성물. According to claim 1,
The photosensitive resin composition in which the said copolymer (A) further contains the structural unit (d) which has a hydroxyl group.
상기 공중합체 (A) 가, 메타크릴산2-(3,5-디메틸피라졸-1-일)카르보닐아미노에틸, 메타크릴산2-[O-(1'-메틸프로필리덴아미노)카르복시아미노]에틸, 말론산-2-[[[2-메틸-1-옥소-2-프로페닐]옥시]에틸]아미노]카르보닐]-1,3디에틸에스테르, 벤조산-4-[[[[2-[(2-메틸-1-옥소-2-프로펜-1-일)옥시]에틸]아미노]카르보닐]옥시]메틸에스테르, 벤조산-2-[[[[2-[(2-메틸-1-옥시-2-프로펜-1-일)옥시]에틸]아미노]카르보닐]옥시]메틸에스테르 및 2-프로펜산-2-메틸-2-[[(3,5-디메틸페녹시)카르보닐]아미노]에틸에스테르로 이루어지는 군에서 선택되는 적어도 1 종 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜(메트)아크릴레이트 유래의 구성 단위 (c) 와, 2-하이드록시에틸메타크릴레이트 유래의 구성 단위 (d) 와, 디시클로펜타닐(메트)아크릴레이트 및 메틸(메트)아크릴레이트로 이루어지는 군에서 선택되는 적어도 1 종 유래의 구성 단위 (e) 를 함유하는 감광성 수지 조성물.According to claim 5,
The copolymer (A) is methacrylic acid 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl, methacrylic acid 2-[O-(1'-methylpropylideneamino)carboxyamino ]ethyl, malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, benzoic acid-4-[[[[2 -[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2-methyl- 1-oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methylester and 2-propenoic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carb A structural unit (a) derived from at least one selected from the group consisting of bornyl] amino] ethyl ester, a structural unit (b) derived from (meth)acrylic acid, and a structural unit derived from glycidyl (meth)acrylate ( c), a structural unit derived from 2-hydroxyethyl methacrylate (d), and a structural unit derived from at least one selected from the group consisting of dicyclopentanyl (meth)acrylate and methyl (meth)acrylate ( A photosensitive resin composition containing e).
상기 공중합체 (A) 가, 메타크릴산2-[O-(1'-메틸프로필리덴아미노)카르복시아미노]에틸 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜(메트)아크릴레이트 유래의 구성 단위 (c) 와, 디시클로펜타닐(메트)아크릴레이트 유래의 구성 단위 (e) 를 함유하는 감광성 수지 조성물.According to claim 4,
The copolymer (A) is a structural unit (a) derived from methacrylic acid 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl, a structural unit (b) derived from (meth)acrylic acid, and , The photosensitive resin composition containing the structural unit (c) derived from glycidyl (meth)acrylate, and the structural unit (e) derived from dicyclopentanyl (meth)acrylate.
상기 공중합체 (A) 가, 메타크릴산2-(3,5-디메틸피라졸-1-일)카르보닐아미노에틸 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜(메트)아크릴레이트 유래의 구성 단위 (c) 와, 디시클로펜타닐(메트)아크릴레이트 유래의 구성 단위 (e) 를 함유하는 감광성 수지 조성물.According to claim 4,
The copolymer (A) contains a structural unit (a) derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylic acid and a structural unit (b) derived from (meth)acrylic acid and a structural unit (c) derived from glycidyl (meth)acrylate and a structural unit (e) derived from dicyclopentanyl (meth)acrylate.
상기 공중합체 (A) 가, 메타크릴산2-(3,5-디메틸피라졸-1-일)카르보닐아미노에틸 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜(메트)아크릴레이트 유래의 구성 단위 (c) 와, 2-하이드록시에틸메타크릴레이트 유래의 구성 단위 (d) 와, 디시클로펜타닐(메트)아크릴레이트 유래의 구성 단위 (e) 를 함유하는 감광성 수지 조성물.According to claim 5,
The copolymer (A) contains a structural unit (a) derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylic acid and a structural unit (b) derived from (meth)acrylic acid and a structural unit (c) derived from glycidyl (meth)acrylate, a structural unit (d) derived from 2-hydroxyethyl methacrylate, and a structural unit (e) derived from dicyclopentanyl (meth)acrylate ) Photosensitive resin composition containing.
상기 공중합체 (A) 가, 말론산-2-[[[2-메틸-1-옥소-2-프로페닐]옥시]에틸]아미노]카르보닐]-1,3디에틸에스테르 유래의 구성 단위 (a) 와, (메트)아크릴산 유래의 구성 단위 (b) 와, 글리시딜(메트)아크릴레이트 유래의 구성 단위 (c) 와, 디시클로펜타닐(메트)아크릴레이트 유래의 구성 단위 (e) 를 함유하는 감광성 수지 조성물.According to claim 4,
The copolymer (A) is a structural unit derived from malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester ( a), (meth)acrylic acid-derived structural unit (b), glycidyl (meth)acrylate-derived structural unit (c), and dicyclopentanyl (meth)acrylate-derived structural unit (e) Photosensitive resin composition containing.
상기 공중합체 (A) 가, 수산기를 갖는 구성 단위 (d) 및 상기 구성 단위 (a) ∼ (d) 이외의 구성 단위 (e) 를 추가로 함유하고,
상기 공중합체 (A) 가, 상기 블록 이소시아나토기를 갖는 구성 단위 (a) 를 1 ∼ 40 몰%, 상기 산기를 갖는 구성 단위 (b) 를 1 ∼ 60 몰%, 상기 에폭시기를 갖는 구성 단위 (c) 를 1 ∼ 70 몰%, 상기 수산기를 갖는 구성 단위 (d) 를 0 몰% 초과 ∼ 50 몰% 및 상기 구성 단위 (e) 를 0 몰% 초과 ∼ 80 몰% 함유하는 감광성 수지 조성물.According to claim 1,
The copolymer (A) further contains a structural unit (d) having a hydroxyl group and a structural unit (e) other than the structural units (a) to (d),
The copolymer (A) contains 1 to 40 mol% of the structural unit (a) having the block isocyanato group, 1 to 60 mol% of the structural unit (b) having the acid group, and the structural unit having the epoxy group The photosensitive resin composition containing 1-70 mol% of (c), more than 0 mol% - 50 mol% of the structural unit (d) which has the said hydroxyl group, and more than 0 mol% - 80 mol% of the said structural unit (e).
상기 공중합체 (A) 가, 수산기를 갖는 구성 단위 (d) 및 상기 구성 단위 (a) ∼ (d) 이외의 구성 단위 (e) 를 추가로 함유하고,
상기 공중합체 (A) 가, 상기 블록 이소시아나토기를 갖는 구성 단위 (a) 를 3 ∼ 20 몰%, 상기 산기를 갖는 구성 단위 (b) 를 20 ∼ 50 몰%, 상기 에폭시기를 갖는 구성 단위 (c) 를 20 ∼ 40 몰%, 상기 수산기를 갖는 구성 단위 (d) 를 0 몰% 초과 ∼ 20 몰% 및 상기 구성 단위 (e) 를 20 ∼ 40 몰% 함유하는 감광성 수지 조성물.According to claim 1,
The copolymer (A) further contains a structural unit (d) having a hydroxyl group and a structural unit (e) other than the structural units (a) to (d),
The copolymer (A) contains 3 to 20 mol% of the structural unit (a) having the block isocyanato group, 20 to 50 mol% of the structural unit (b) having the acid group, and the structural unit having the epoxy group The photosensitive resin composition containing 20-40 mol% of (c), more than 0 mol% - 20 mol% of the structural unit (d) which has the said hydroxyl group, and 20-40 mol% of the said structural unit (e).
상기 공중합체 (A) 와 상기 반응성 희석제 (C) 의 합계량 100 질량부에 대하여, 상기 공중합체 (A) 가 10 ∼ 100 질량부, 상기 용제 (B) 가 30 ∼ 1,000 질량부, 상기 반응성 희석제 (C) 가 0 질량부 초과 ∼ 90 질량부, 상기 광 중합 개시제 (D) 가 0.1 ∼ 30 질량부, 상기 착색제 (E) 가 3 ∼ 80 질량부 함유되는 감광성 수지 조성물.According to claim 13,
10 to 100 parts by mass of the copolymer (A), 30 to 1,000 parts by mass of the solvent (B), and the reactive diluent ( The photosensitive resin composition in which C) contains more than 0 mass part - 90 mass parts, 0.1-30 mass parts of the said photoinitiator (D), and 3-80 mass parts of the said coloring agent (E).
상기 용제 (B) 가, 수산기 함유 유기 용제를 포함하는 감광성 수지 조성물.According to claim 13,
The photosensitive resin composition in which the said solvent (B) contains the organic solvent containing a hydroxyl group.
상기 착색제 (E) 가, 안료를 포함하는 감광성 수지 조성물.According to claim 13,
The photosensitive resin composition in which the said coloring agent (E) contains a pigment.
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