TWI810722B - Pigment dispersion liquid, colored photosensitive resin composition, liquid crystal display device and organic light emitting device containing the same - Google Patents
Pigment dispersion liquid, colored photosensitive resin composition, liquid crystal display device and organic light emitting device containing the same Download PDFInfo
- Publication number
- TWI810722B TWI810722B TW110143807A TW110143807A TWI810722B TW I810722 B TWI810722 B TW I810722B TW 110143807 A TW110143807 A TW 110143807A TW 110143807 A TW110143807 A TW 110143807A TW I810722 B TWI810722 B TW I810722B
- Authority
- TW
- Taiwan
- Prior art keywords
- pigment dispersion
- dispersion liquid
- resin composition
- photosensitive resin
- colored photosensitive
- Prior art date
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- 239000000049 pigment Substances 0.000 title claims abstract description 90
- 239000006185 dispersion Substances 0.000 title claims abstract description 86
- 239000007788 liquid Substances 0.000 title claims abstract description 46
- 239000011342 resin composition Substances 0.000 title claims abstract description 41
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 21
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 28
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims description 40
- 239000000126 substance Substances 0.000 claims description 30
- 125000006850 spacer group Chemical group 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 18
- 239000002270 dispersing agent Substances 0.000 claims description 14
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 230000003287 optical effect Effects 0.000 abstract description 13
- 230000003746 surface roughness Effects 0.000 abstract description 11
- 230000000704 physical effect Effects 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 description 27
- 238000000034 method Methods 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 9
- 230000001976 improved effect Effects 0.000 description 9
- VAPKHDZBJXRVNG-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene;1-ethenyl-4-methylbenzene Chemical group CC1=CC=C(C=C)C=C1.CC1=CC=CC(C=C)=C1 VAPKHDZBJXRVNG-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- OXFVQQBWUCAVDM-UHFFFAOYSA-N 1-phenylsulfanylethyl prop-2-enoate Chemical compound C=CC(=O)OC(C)SC1=CC=CC=C1 OXFVQQBWUCAVDM-UHFFFAOYSA-N 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- -1 N,N-dimethylaminoethyl Chemical group 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000011325 microbead Substances 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- LZDDXRWBWZUFHD-ODZAUARKSA-N (z)-but-2-enedioic acid;2-methylprop-1-ene Chemical compound CC(C)=C.OC(=O)\C=C/C(O)=O LZDDXRWBWZUFHD-ODZAUARKSA-N 0.000 description 1
- CNJRPYFBORAQAU-UHFFFAOYSA-N 1-ethoxy-2-(2-methoxyethoxy)ethane Chemical compound CCOCCOCCOC CNJRPYFBORAQAU-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- RWHRFHQRVDUPIK-UHFFFAOYSA-N 50867-57-7 Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O RWHRFHQRVDUPIK-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002551 Fe-Mn Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SEEVRZDUPHZSOX-WPWMEQJKSA-N [(e)-1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino] acetate Chemical compound C=1C=C2N(CC)C3=CC=C(C(\C)=N\OC(C)=O)C=C3C2=CC=1C(=O)C1=CC=CC=C1C SEEVRZDUPHZSOX-WPWMEQJKSA-N 0.000 description 1
- KVXNKFYSHAUJIA-UHFFFAOYSA-N acetic acid;ethoxyethane Chemical compound CC(O)=O.CCOCC KVXNKFYSHAUJIA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/002—Pigment pastes, e.g. for mixing in paints in organic medium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- 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
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1339—Gaskets; Spacers; Sealing of cells
- G02F1/13398—Spacer materials; Spacer properties
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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Abstract
Description
本發明關於在液晶顯示器用黑色矩陣、柱狀間隔物、黑色柱狀間隔物(BCS，遮光性間隔物)及有機發光器件用黑堤等的製作中使用的顏料分散液(漆漿，mill base)及包含其的著色光敏樹脂組合物。 The present invention relates to the pigment dispersion liquid (paint paste, mill base) used in the production of black matrix for liquid crystal display, columnar spacer, black columnar spacer (BCS, light-shielding spacer) and organic light-emitting device black bank etc. ) and a colored photosensitive resin composition comprising the same.
液晶顯示裝置(liquid crystal display，LCD)作為在移動設備、電腦顯示器及HDTV等中利用的顯示裝置受到矚目。在液晶顯示裝置的液晶單元中，為了恆定維持上下透明基板之間的間隔而適用使用光敏樹脂組合物來形成的柱狀間隔物。這種柱狀間隔物在基板上塗敷光敏樹脂組合物，使用光罩曝光光化射線等之後，藉由進行顯影和固化的方法製作。 A liquid crystal display (liquid crystal display, LCD) is attracting attention as a display device used in mobile devices, computer monitors, HDTVs, and the like. In a liquid crystal cell of a liquid crystal display device, in order to maintain a constant distance between upper and lower transparent substrates, a columnar spacer formed using a photosensitive resin composition is applied. Such a columnar spacer is produced by coating a photosensitive resin composition on a substrate, exposing it to actinic rays or the like using a photomask, and then developing and curing it.
另一方面，需要開發即使在使用柔性有機發光二極體的智能手機(smart phone)、平板電腦(tablet)等中小型智能設備(smart device)不使用偏光膜，也能夠有效地減少外光反射，將可以改善對比度及光效的堤形成為黑色的材料及過程。這種黑堤可以改善有機發光二極體(OLED)的可視性，可以執行有機發光二極體的堤作用並執行黑色矩陣作用，因此，可以實現無 偏光板(Pol-less)、無黑色矩陣(BM-less)有機發光二極體器件化，從而簡化製作過程。結果，在使用黑堤的情況下，可以確保價格競爭力，從而適用黑堤等技術作為在有機發光二極體市場中有用的新技術受到矚目。 On the other hand, it is necessary to develop a technology that can effectively reduce external light reflection even without using a polarizing film in small and medium-sized smart devices (smart devices) such as smart phones and tablets that use flexible organic light-emitting diodes. , The material and process of forming the bank that can improve the contrast and light effect into black. This black bank can improve the visibility of the organic light-emitting diode (OLED), can perform the bank function of the organic light-emitting diode and perform the black matrix function, and therefore, can realize the Polarizing plate (Pol-less), no black matrix (BM-less) organic light-emitting diode device, thus simplifying the manufacturing process. As a result, when black banks are used, price competitiveness can be secured, and technology such as application of black banks has attracted attention as a useful new technology in the organic light emitting diode market.
對此，執行對於有效地用於液晶顯示器用黑色矩陣、柱狀間隔物及黑色柱狀間隔物及有機發光二極體用黑堤等的製作，可體現精巧的微細圖案的正型著色光敏樹脂組合物的研究(韓國公開專利第10-2002-0021005號)。 In response to this, positive-type colored photosensitive resins that can express fine and fine patterns are effectively used in the production of black matrices for liquid crystal displays, columnar spacers, black columnar spacers, and black banks for organic light-emitting diodes. Composition Research (Korean Laid-Open Patent No. 10-2002-0021005).
但是，這種著色光敏樹脂組合物存在如下的問題，即，著色顏料的分散能力及分散穩定性低，穩定性不良，與鹼溶性樹脂的相容性差，當將上述著色光敏樹脂組合物適用於液晶顯示器或有機發光二極體等的顯示器件時，在顯影步驟之後，在黑色圖案周圍剩留作為顏料分散液殘留物的殘渣，從而降低顯示器件的性能及壽命特性。 However, this colored photosensitive resin composition has the following problems, that is, the dispersibility and dispersion stability of the colored pigment are low, the stability is poor, and the compatibility with the alkali-soluble resin is poor. When the above colored photosensitive resin composition is applied to In the case of display devices such as liquid crystal displays or organic light-emitting diodes, after the development step, residues as pigment dispersion residues remain around the black pattern, thereby reducing the performance and life characteristics of the display device.
並且，為了提高上述顯示器件的可靠性及耐久性，黑色矩陣、柱狀間隔物及黑色柱狀間隔物等應具備優秀的光學密度及黏度穩定性，不僅如此，當形成微細圖案時應具備優秀的緊貼性。 Moreover, in order to improve the reliability and durability of the above-mentioned display device, the black matrix, the columnar spacer, and the black columnar spacer should have excellent optical density and viscosity stability, not only that, but also should have excellent stability when forming fine patterns. of closeness.
現有技術文獻 prior art literature
專利文獻 patent documents
專利文獻1：韓國公開專利第10-2002-0021005號。 Patent Document 1: Korean Laid-Open Patent No. 10-2002-0021005.
本發明的目的在於，提供如下的顏料分散液及包含其的著色光敏樹脂組合物，即，光學密度、黏度穩定性、表面粗糙度等的物性優秀，不僅如此，可形成具有優秀的緊貼性的固化膜，進而，在適用於顯示器件的 情況下，在顯影步驟之後，改善黑色圖案周圍的圖案殘渣特性，從而可以進一步提高顯示器件的耐久性、壽命特性及可靠性。 The object of the present invention is to provide a pigment dispersion liquid and a colored photosensitive resin composition containing the same, that is, excellent in physical properties such as optical density, viscosity stability, and surface roughness, and not only that, but also excellent in adhesion. The cured film, in turn, is suitable for display devices In this case, after the developing step, the pattern residue characteristics around the black pattern are improved, so that the durability, lifetime characteristics, and reliability of the display device can be further improved.
本發明提供顏料分散液，上述顏料分散液包含顏料、黏結劑、分散劑及溶劑，上述黏結劑包含具有以下化學式1至化學式5的多個單體的共聚物的丙烯酸樹脂。 The present invention provides a pigment dispersion. The pigment dispersion includes a pigment, a binder, a dispersant, and a solvent. The binder includes an acrylic resin of a copolymer of monomers having the following chemical formulas 1 to 5.
並且，本發明提供顏料分散液，上述顏料分散液包含顏料、黏結劑、分散劑及溶劑，上述黏結劑包含具有以下化學式2至化學式5的多個單體的共聚物的丙烯酸樹脂。 In addition, the present invention provides a pigment dispersion comprising a pigment, a binder, a dispersant, and a solvent, wherein the binder comprises an acrylic resin having a copolymer of a plurality of monomers of the following chemical formulas 2 to 5.
並且，本發明提供包含上述顏料分散液、光聚合化合物、光聚合引發劑及溶劑的著色光敏樹脂組合物。 Furthermore, the present invention provides a colored photosensitive resin composition comprising the above-mentioned pigment dispersion, a photopolymerization compound, a photopolymerization initiator, and a solvent.
同時，本發明提供固化上述著色光敏樹脂組合物來製備的液晶顯示裝置用黑色柱狀間隔物。 Meanwhile, the present invention provides a black columnar spacer for liquid crystal display devices prepared by curing the above-mentioned colored photosensitive resin composition.
進而，本發明提供固化上述著色光敏樹脂組合物來製備的有機發光器件用黑堤。 Furthermore, the present invention provides a black bank for an organic light-emitting device prepared by curing the above-mentioned colored photosensitive resin composition.
本發明實例的顏料分散液及包含其的著色光敏樹脂組合物的光學密度、黏度穩定性、表面粗糙度等的物性優秀，不僅如此，可形成具有優秀的緊貼性的固化膜，進而，從上述顏料分散液及包含其的著色光敏樹脂組合物製作的液晶顯示器及有機發光二極體等的顯示器件在顯影步驟之後，顯著減少在黑色圖案周圍的作為顏料分散液殘留物的殘渣，從而，與以往相比，具有卓越優秀的耐久性、壽命特性及可靠性。 The pigment dispersion liquid of the example of the present invention and the colored photosensitive resin composition containing it are excellent in physical properties such as optical density, viscosity stability, and surface roughness, and not only that, but also can form a cured film with excellent adhesion, and further, from The above-mentioned pigment dispersion liquid and the colored photosensitive resin composition comprising the liquid crystal display and display devices such as organic light-emitting diodes, after the development step, significantly reduce the residue as the pigment dispersion liquid residue around the black pattern, thereby, Compared with the past, it has excellent durability, life characteristics and reliability.
圖1示出當利用實施例1及比較例2和比較例3的著色光敏樹脂組合物來適用於有機發光器件用黑堤時，在顯影步驟之後，確認黑色圖案周圍是否殘留殘渣的掃描電子顯微鏡(SEM)測定結果。 Fig. 1 shows a scanning electron microscope for confirming whether residues remain around the black pattern after the development step when the colored photosensitive resin compositions of Example 1 and Comparative Examples 2 and 3 are applied to black banks for organic light-emitting devices (SEM) measurement results.
本發明提供顏料分散液(漆漿)，上述顏料分散液包含顏料、黏結劑、分散劑及溶劑，上述黏結劑包含具有以下化學式1至化學式5的多個單體的共聚物的丙烯酸樹脂。 The present invention provides a pigment dispersion (millbase). The pigment dispersion includes a pigment, a binder, a dispersant, and a solvent. The binder includes an acrylic resin that is a copolymer of a plurality of monomers having the following chemical formulas 1 to 5.
化學式2：
上述黏結劑包含聚合化學式1的單體(甲基丙烯酸苄酯，BzMA)、化學式2的單體(甲基丙烯酸，MAA)、化學式3的單體(苯硫基乙醇丙烯酸酯，PTEA)、化學式4的單體(乙烯基甲苯單體，VTM)及化學式5的單體(甲基丙烯酸四氫糠酯，THFMA)來獲取的丙烯酸樹脂，在顯影步驟中是體現顯影性的鹼顯影性高分子，並且，起到在塗敷之後形成塗膜的基礎作用及體現最終圖案的結構物作用。 The above-mentioned binder comprises monomers of chemical formula 1 (benzyl methacrylate, BzMA), monomers of chemical formula 2 (methacrylic acid, MAA), monomers of chemical formula 3 (phenylthioethanol acrylate, PTEA), chemical formula 4 monomer (vinyl toluene monomer, VTM) and chemical formula 5 monomer (tetrahydrofurfuryl methacrylate, THFMA) to obtain an acrylic resin, which is an alkali-developable polymer that exhibits developability in the developing step , And, it plays the basic role of forming a coating film after coating and the role of a structure that embodies the final pattern.
本發明實例的顏料分散液的初始黏度及在常溫條件下的黏度穩定性優秀，包含其的著色光敏樹脂組合物的光學密度、表面粗糙度等的物性優秀，不僅如此，可形成具有優秀的緊貼性的固化膜。 The pigment dispersion liquid of the example of the present invention has excellent initial viscosity and viscosity stability under normal temperature conditions, and the optical density, surface roughness and other physical properties of the colored photosensitive resin composition containing it are excellent. Adhesive cured film.
尤其，在上述顏料分散液中，黏結劑包含化學式1的單體(甲基丙烯酸苄酯，BzMA)，由此，可以進一步改善在常溫條件下的黏度穩定性， 在將包含其的著色光敏樹脂組合物用於液晶顯示器用黑色矩陣、柱狀間隔物及黑色柱狀間隔物及有機發光二極體用黑堤等的製備的情況下，在顯影步驟之後，顯著減少在黑色圖案周圍的作為顏料分散液殘留物的殘渣，從而，可體現與以往相比，具有卓越優秀的耐久性、壽命特性及可靠性的液晶顯示器或有機發光二極體。 In particular, in the above-mentioned pigment dispersion liquid, the binder includes the monomer of chemical formula 1 (benzyl methacrylate, BzMA), thereby, the viscosity stability under normal temperature conditions can be further improved, When the colored photosensitive resin composition containing it is used in the preparation of black matrixes for liquid crystal displays, columnar spacers and black columnar spacers, and black banks for organic light-emitting diodes, after the developing step, the By reducing the residue that is the pigment dispersion liquid residue around the black pattern, it is possible to realize a liquid crystal display or an organic light-emitting diode that has excellent durability, life characteristics, and reliability compared to the past.
並且，上述黏結劑有可能不包含甲基丙烯酸縮水甘油酯(GMA)。由於上述黏結劑不包含甲基丙烯酸縮水甘油酯(GMA)，由此，當將所製備的顏料分散液適用於液晶顯示器或有機發光二極體時，可以進一步提高在顯影步驟之後的黑色圖案周圍的殘渣減少效果等。 In addition, the above-mentioned binder may not contain glycidyl methacrylate (GMA). Since the above-mentioned binder does not contain glycidyl methacrylate (GMA), when the prepared pigment dispersion liquid is applied to a liquid crystal display or an organic light-emitting diode, it is possible to further improve the surrounding area of the black pattern after the developing step. residue reduction effect, etc.
以構成丙烯酸樹脂的重複單元的總莫耳數為基準，上述丙烯酸樹脂能夠以1：2至10：1至20：2至20：1至30的莫耳比包含分別從上述化學式1至化學式5的單體衍生的重複單元(1)至重複單元(5)。具體地，以構成丙烯酸樹脂的重複單元的總莫耳數為基準，上述丙烯酸樹脂能夠以1：2至4：1至6：2至5：1至6的莫耳比包含重複單元(1)至(5)。當處於上述範圍時，可以維持顯影性並提高與基板的緊貼性，可提高在顯影步驟之後的黑色圖案周圍的殘渣減少效果等。 Based on the total number of moles of repeating units constituting the acrylic resin, the above-mentioned acrylic resin can contain the above chemical formula 1 to chemical formula 5 at a molar ratio of 1:2 to 10:1 to 20:2 to 20:1 to 30, respectively. Monomer-derived repeating unit (1) to repeating unit (5) of . Specifically, the above-mentioned acrylic resin can contain the repeating unit (1) in a molar ratio of 1:2 to 4:1 to 6:2 to 5:1 to 6 based on the total number of moles of repeating units constituting the acrylic resin to (5). When it exists in the said range, the adhesiveness with a board|substrate can be improved maintaining developability, and the residue reduction effect etc. around the black pattern after a developing process can be improved.
可藉由使上述化學式1至化學式5的化合物根據通常的方法進行聚合反應來製備需要的丙烯酸樹脂。例如，在氮氣氛下，在60至120℃的溫度條件下使化學式1至化學式5的化合物進行聚合反應來製備需要的丙烯酸樹脂。 The desired acrylic resin can be prepared by polymerizing the compounds of the above-mentioned Chemical Formula 1 to Chemical Formula 5 according to a general method. For example, the desired acrylic resin is prepared by polymerizing the compounds of Chemical Formula 1 to Chemical Formula 5 at a temperature of 60 to 120° C. under a nitrogen atmosphere.
如上所述，所獲取的丙烯酸樹脂的重均分子量(Mw)可以為3000g/mol至20000g/mol，具體地，5000g/mol至15000g/mol或6000g/mol至12000g/mol。並且，上述丙烯酸樹脂的酸值可以為50KOHmg/g至 130KOHmg/g，具體地，可以為50KOHmg/g至80KOHmg/g或60至70KOHmg/g。 As mentioned above, the obtained acrylic resin may have a weight average molecular weight (Mw) of 3000 g/mol to 20000 g/mol, specifically, 5000 g/mol to 15000 g/mol or 6000 g/mol to 12000 g/mol. And, the acid value of above-mentioned acrylic resin can be 50KOHmg/g to 130KOHmg/g, specifically, may be 50KOHmg/g to 80KOHmg/g or 60 to 70KOHmg/g.
可將上述丙烯酸樹脂與顏料、分散劑及溶劑混合之後進行密封，由此可以製備本發明的顏料分散液。 The pigment dispersion liquid of the present invention can be prepared by mixing the above-mentioned acrylic resin with a pigment, a dispersant, and a solvent and then sealing it.
以分散液總重量為基準，上述顏料分散液可以包含5至25重量百分比量的顏料。並且，以100重量份的顏料為基準，顏料分散液可以包含1重量份至80重量份的分散劑、1重量份至80重量份的黏結劑及10重量份至150重量份的溶劑。 Based on the total weight of the dispersion liquid, the above-mentioned pigment dispersion liquid may contain 5 to 25 weight percent of the pigment. Furthermore, based on 100 parts by weight of the pigment, the pigment dispersion liquid may include 1 to 80 parts by weight of a dispersant, 1 to 80 parts by weight of a binder, and 10 to 150 parts by weight of a solvent.
接著，在上述含量範圍內，可以使用珠磨機(bead)、磨碎機(attriter)、超級磨機、均質混合機、油漆振動器(paint shaker)、球磨機、砂磨機或臥式磨機來研磨混合對應原料的原料混合物。例如，利用0.5mm至1.2mm的比較大的珠磨機來第一次研磨原料混合物，由此，將原料混合物內的巨大凝集粒子均質化(第一次分散過程)，利用0.3mm至0.05mm的微小珠磨機來對第一次研磨的原料混合物進行第二次研磨，由此可以將原料混合物內的粒子微細化(第二次分散過程)(設備：油漆振動器)。 Next, within the above content range, a bead mill, attriter, super mill, homomixer, paint shaker, ball mill, sand mill or horizontal mill may be used to grind and mix the raw material mixture corresponding to the raw material. For example, use a relatively large bead mill of 0.5mm to 1.2mm to grind the raw material mixture for the first time, thereby homogenizing the huge aggregated particles in the raw material mixture (the first dispersion process), and use a 0.3mm to 0.05mm The micro-bead mill is used to grind the raw material mixture for the first time, so that the particles in the raw material mixture can be miniaturized (the second dispersion process) (equipment: paint vibrator).
並且，可將完成分散的顏料分散液熟成規定時間，例如，24小時至168小時來實現分散的穩定化。 In addition, the dispersed pigment dispersion can be matured for a predetermined period of time, for example, 24 hours to 168 hours to stabilize the dispersion.
上述顏料、分散劑及溶劑可以使用一般的材料。 General materials can be used for the above-mentioned pigments, dispersants and solvents.
例如，作為顏料的具體例，可以為炭黑、鈦黑、Cu-Fe-Mn基氧化物、合成鐵黑、苯胺黑、內醯胺黑、苝黑、C.I顏料藍、C.I顏料紅、C.I顏料綠及它們的混合物，但並不局限於此。 For example, specific examples of pigments include carbon black, titanium black, Cu-Fe-Mn based oxides, synthetic iron black, aniline black, lactam black, perylene black, C.I pigment blue, C.I pigment red, C.I pigment Green and their mixtures, but not limited to.
作為分散劑的具體例，可以為如(甲基)丙烯酸丁酯、(甲基)丙烯酸N,N-二甲氨基乙酯等丙烯酸酯的分散劑；苯乙烯-丙烯酸樹脂、苯乙烯-甲基丙烯酸樹脂、苯乙烯-丙烯酸-丙烯酸酯樹脂、苯乙烯-馬來酸樹脂、 苯乙烯-丙烯酸-丙烯酸酯樹脂、苯乙烯-馬來酸酯樹脂、甲基丙烯酸-甲基丙烯酸酯樹脂、丙烯酸-丙烯酸酯樹脂、異丁烯-馬來酸樹脂、乙烯基酯樹脂等的含乙烯雙鍵的樹脂；聚氨酯、聚羧酸酯、不飽和聚醯胺、聚羧酸、聚矽氧烷、(甲基)丙烯酸-苯乙烯共聚物、(甲基)丙烯酸-(甲基)丙烯酸酯共聚物、聚乙烯醇、聚乙烯吡咯烷酮、聚酯、改性聚丙烯酸酯、磷酸酯、聚羧酸等的樹脂類分散劑及它們的混合物，但並不局限於此。 Specific examples of dispersants include acrylate dispersants such as butyl (meth)acrylate and N,N-dimethylaminoethyl (meth)acrylate; styrene-acrylic resins, styrene-methyl acrylic resin, styrene-acrylic-acrylate resin, styrene-maleic resin, Styrene-acrylic-acrylate resins, styrene-maleate resins, methacrylic acid-methacrylate resins, acrylic-acrylate resins, isobutylene-maleic acid resins, vinyl ester resins, etc. bonded resin; polyurethane, polycarboxylate, unsaturated polyamide, polycarboxylate, polysiloxane, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer Resin dispersants such as polyvinyl alcohol, polyvinyl pyrrolidone, polyester, modified polyacrylate, phosphoric acid ester, polycarboxylic acid, and mixtures thereof, but are not limited thereto.
作為溶劑的具體例，可以為二乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚等的(聚)亞烷基二醇單烷基醚類；乙二醇單甲醚醋酸酯、乙二醇單乙醚醋酸酯、丙二醇單甲醚醋酸酯、丙二醇單乙醚醋酸酯等的(聚)亞烷基二醇單烷基醚乙酸酯類；二乙二醇單乙醚、二乙二醇甲乙醚、四氫呋喃等的乙醚類；甲基乙基酮、甲基異丁基酮、環己酮、2-庚酮、3-庚酮等的酮類；乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、二乙二醇、甘油等的醇類及它們的混合物，但並不局限於此。 Specific examples of solvents include (poly)alkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates such as alcohol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol monoethyl ether, diethylene glycol methyl ethyl ether, Diethyl ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; ethanol, propanol, butanol, hexanol, cyclohexane Alcohols such as alcohol, ethylene glycol, diethylene glycol, glycerin, and mixtures thereof, but are not limited thereto.
根據需要，上述顏料分散液還可包含幫助分散劑的作用來縮減顏料分散液的分散時間，起到更加穩定地維持顏料分散液的黏度的作用的分散助劑。上述分散助劑可以使用一般的材料。並且，以100重量份的顏料為基準，顏料分散液可包含1重量份至10重量份量的分散助劑。 If necessary, the above-mentioned pigment dispersion liquid may further contain a dispersing aid that assists the action of the dispersant to shorten the dispersion time of the pigment dispersion liquid and maintain the viscosity of the pigment dispersion liquid more stably. General materials can be used for the above-mentioned dispersing aids. Also, based on 100 parts by weight of the pigment, the pigment dispersion liquid may include 1 to 10 parts by weight of the dispersion aid.
本發明的顏料分散液的平均粒徑可以為90nm至250nm，例如，90nm至120nm，之後，可以形成表面粗糙度光滑的固化膜。並且，在25℃(常溫)條件下，顏料分散液呈現出2cps至8cps、2cps至6cps、2cps至5cps、2cps至4cps或2cps至3.7cps的黏度，當在25℃(常溫)條件下維持7日時，可以呈現出105%以下，具體地，95%至105%、98%至105%、98%至103%或100%至103%的黏度變化率。 The average particle diameter of the pigment dispersion liquid of the present invention may be 90nm to 250nm, for example, 90nm to 120nm, and then a cured film with smooth surface roughness may be formed. Moreover, at 25°C (normal temperature), the pigment dispersion exhibits a viscosity of 2cps to 8cps, 2cps to 6cps, 2cps to 5cps, 2cps to 4cps or 2cps to 3.7cps, when maintained at 25°C (normal temperature) for 7 Over time, it may exhibit a viscosity change rate of 105% or less, specifically, 95% to 105%, 98% to 105%, 98% to 103%, or 100% to 103%.
在上述顏料分散液的黏度變化率滿足上述範圍的情況下，在常溫條件下的儲存穩定性優秀，從而可以體現出利用上述顏料分散液的著色光敏樹脂組合物的物性和顯示器件的壽命特性等優秀的性能。 When the viscosity change rate of the above-mentioned pigment dispersion liquid satisfies the above-mentioned range, the storage stability under normal temperature conditions is excellent, so that the physical properties of the colored photosensitive resin composition using the above-mentioned pigment dispersion liquid and the life characteristics of the display device can be reflected. excellent performance.
本發明另一實例的顏料分散液包含顏料、黏結劑、分散劑及溶劑，上述黏結劑包含具有上述化學式2至化學式5的多個單體的共聚物的丙烯酸樹脂。 The pigment dispersion liquid of another example of the present invention includes a pigment, a binder, a dispersant, and a solvent, and the binder includes an acrylic resin having a copolymer of a plurality of monomers of the above chemical formula 2 to chemical formula 5.
具體地，上述黏結劑可以包含藉由聚合上述化學式2的單體(甲基丙烯酸，MAA)、上述化學式3的單體(苯硫基乙醇丙烯酸酯，PTEA)、上述化學式4的單體(乙烯基甲苯單體，VTM)及上述化學式5的單體(甲基丙烯酸四氫糠酯，THFMA)來獲得的丙烯酸樹脂。 Specifically, the above binder may comprise monomers of the above chemical formula 2 (methacrylic acid, MAA), monomers of the above chemical formula 3 (phenylthioethanol acrylate, PTEA), monomers of the above chemical formula 4 (ethylene an acrylic resin obtained from a monomer of methyl toluene, VTM) and a monomer of the above chemical formula 5 (tetrahydrofurfuryl methacrylate, THFMA).
並且，上述黏結劑有可能不包含甲基丙烯酸縮水甘油酯(GMA)。由於上述黏結劑不包含甲基丙烯酸縮水甘油酯(GMA)，由此，當將從此製備的顏料分散液適用於液晶顯示器或有機發光二極體時，可以進一步提高在顯影步驟之後的黑色圖案周圍的殘渣降低效果等。 In addition, the above-mentioned binder may not contain glycidyl methacrylate (GMA). Since the above-mentioned binder does not contain glycidyl methacrylate (GMA), when the pigment dispersion prepared therefrom is applied to a liquid crystal display or an organic light-emitting diode, it is possible to further improve the black pattern periphery after the developing step. residue reduction effect, etc.
以構成丙烯酸樹脂的重複單元的總莫耳數為基準，上述丙烯酸樹脂可以按1：0.2至5：0.5至3：0.5至3的莫耳比包含分別從化學式2至化學式5的單體化合物衍生的重複單元(2)至重複單元(5)。具體地，以構成丙烯酸樹脂的重複單元的總莫耳數為基準，上述丙烯酸樹脂可按1：0.2至3：0.5至2：0.5至2的莫耳比包含重複單元(2)至重複單元(5)。當處於上述範圍時，可以維持顯影性並提高與基板的緊貼性，可提高在顯影步驟之後的黑色圖案周圍的殘渣減少效果等。 Based on the total number of moles of repeating units constituting the acrylic resin, the above-mentioned acrylic resin may contain monomer compounds derived from Chemical Formula 2 to Chemical Formula 5 at a molar ratio of 1:0.2 to 5:0.5 to 3:0.5 to 3, respectively. Repeating unit (2) to repeating unit (5) of . Specifically, based on the total number of moles of repeating units constituting the acrylic resin, the above-mentioned acrylic resin may comprise the repeating unit (2) to the repeating unit ( 5). When it exists in the said range, the adhesiveness with a board|substrate can be improved maintaining developability, and the residue reduction effect etc. around the black pattern after a developing process can be improved.
上述丙烯酸樹脂及包含其的顏料分散液的具體組合及物性如上。 The specific composition and physical properties of the acrylic resin and the pigment dispersion liquid containing it are as above.
另一方面，本發明另一實例的著色光敏樹脂組合物包含上述顏料分散液、光聚合化合物、光聚合引發劑及溶劑，根據需要，還可包含鹼顯影性黏結劑樹脂、表面活性劑、矽烷偶聯劑、抗氧劑、穩定劑、均染劑等。 On the other hand, the colored photosensitive resin composition according to another example of the present invention includes the above-mentioned pigment dispersion liquid, photopolymerization compound, photopolymerization initiator and solvent, and may also contain alkali-developable binder resin, surfactant, silane Coupling agent, antioxidant, stabilizer, leveling agent, etc.
包含以上的成分的本發明的著色光敏樹脂組合物可藉由均勻地混合上述構成成分的一般的方法製備。上述構成成分的種類即含量也可以在通常使用的範圍內適當選擇。 The colored photosensitive resin composition of the present invention containing the above components can be prepared by a general method of uniformly mixing the above components. The types and contents of the above-mentioned constituents can also be appropriately selected within the ranges generally used.
可藉由固化上述著色光敏樹脂組合物來製備液晶顯示器用柱狀間隔物、黑色矩陣、黑色柱狀間隔物及有機發光二極體用黑堤。 A column spacer for a liquid crystal display, a black matrix, a black column spacer, and a black bank for an organic light emitting diode can be prepared by curing the above-mentioned colored photosensitive resin composition.
上述柱狀間隔物、黑色矩陣、黑色柱狀間隔物或黑堤可根據通常的方法，例如，可經過塗膜形成過程、曝光過程、顯影過程、熱處理過程來製備。 The above-mentioned columnar spacers, black matrix, black columnar spacers, or black banks can be prepared according to common methods, for example, through a coating film forming process, an exposure process, a development process, and a heat treatment process.
在上述塗膜形成步驟中，使用旋塗或狹縫塗法、輥塗法、絲網印刷法、塗抹法等方法來將本發明的著色光敏樹脂組合物以需要的厚度塗敷在經規定預處理的基板上，在70℃至100℃的溫度條件下進行預固化(pre-bake)1分鐘至10分鐘並去除溶劑來形成塗膜。 In the above-mentioned coating film forming step, the colored photosensitive resin composition of the present invention is applied to a predetermined predetermined thickness using methods such as spin coating or slit coating, roll coating, screen printing, and smearing. On the treated substrate, pre-cure (pre-bake) for 1 minute to 10 minutes at a temperature of 70° C. to 100° C. and remove the solvent to form a coating film.
為了在所獲取的上述塗膜形成圖案而放置規定形態的光罩之後照射200nm至500nm的活性射線。在此情況下，為了製備一體型的黑色柱狀間隔物而使用具有透射率不同的圖案的光罩，以可同時體現柱狀間隔物和黑色矩陣。作為用於照射的光源，可以使用低壓汞燈、高壓汞燈、超高壓汞燈、金鹵燈、氬氣雷射器等，根據情況，也可以使用X光、電子射線等。 In order to form a pattern on the acquired said coating film, after placing the photomask of a predetermined form, it irradiates the actinic ray of 200 nm - 500 nm. In this case, a photomask having a pattern with different transmittances is used in order to produce an integrated black columnar spacer, so that the columnar spacer and the black matrix can be expressed simultaneously. As a light source for irradiation, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon lasers, etc. can be used, and X-rays, electron beams, etc. can also be used depending on the case.
在上述曝光步驟中，將碳酸鈉、氫氧化鈉、氫氧化鉀、四甲基氫氧化銨等的鹼性水溶液用作顯影液來溶解及去除不必要的部分，由此僅殘留曝光部分來形成圖案。在180℃至250℃的溫度條件下，將藉由顯影獲取的圖像圖案後固化(post-bake)10分鐘至60分鐘來獲取最終圖案。 In the above-mentioned exposure step, an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, etc. is used as a developing solution to dissolve and remove unnecessary parts, thereby leaving only the exposed parts to form pattern. Under the temperature condition of 180° C. to 250° C., the image pattern obtained by developing is post-baked for 10 minutes to 60 minutes to obtain a final pattern.
本發明的著色光敏樹脂組合物的平均粒徑可以與顏料分散液的平均粒徑類似，例如，可以為90nm至250nm，具體地，可以為90nm至120nm。在此情況下，可以形成表面粗糙度光滑的固化膜。 The average particle diameter of the colored photosensitive resin composition of the present invention may be similar to the average particle diameter of the pigment dispersion liquid, for example, may be 90nm to 250nm, specifically, may be 90nm to 120nm. In this case, a cured film with smooth surface roughness can be formed.
從本發明實例的著色光敏樹脂組合物製備的液晶顯示器及有機發光二極體等的顯示器件在顯影步驟之後，顯著減少在黑色圖案周圍的作為顏料分散液殘留物的殘渣，從而，與以往相比，具有卓越優秀的可靠性及壽命特性。 Display devices such as liquid crystal displays and organic light-emitting diodes prepared from the colored photosensitive resin composition of the example of the present invention significantly reduce the residue as the pigment dispersion residue around the black pattern after the developing step, thereby, compared with the past Ratio, with excellent reliability and life characteristics.
從上述著色光敏樹脂組合物形成的固化膜(黑色柱狀間隔物或黑堤)可具有1.0/μm至3.5/μm的光學密度。並且，在緊貼力方面，現有固化膜具有30μm以上的最小微細圖案大小，相反，從本發明的著色光敏樹脂組合物形成的固化膜(黑色柱狀間隔物或黑堤)可以具有能夠維持30μm以下的微細圖案，具體地，可以維持18μm至30μm的最小微細圖案的顯著優秀的緊貼力。 A cured film (black column spacer or black bank) formed from the above colored photosensitive resin composition may have an optical density of 1.0/μm to 3.5/μm. And, in terms of adhesion, the existing cured film has a minimum fine pattern size of 30 μm or more. On the contrary, the cured film (black columnar spacer or black bank) formed from the colored photosensitive resin composition of the present invention can maintain a thickness of 30 μm. The following fine patterns, specifically, can maintain remarkably excellent adhesion of the smallest fine patterns of 18 μm to 30 μm.
如上製備的黑色柱狀間隔物或黑堤因優秀的物性而可以有效地用於液晶顯示器、有機發光二極體顯示器等電子部件。因此，本發明提供包括上述黑色柱狀間隔物或黑堤的電子部件。 The black columnar spacers or black banks prepared as above can be effectively used in electronic components such as liquid crystal displays and organic light emitting diode displays due to their excellent physical properties. Therefore, the present invention provides an electronic component including the above-mentioned black columnar spacer or black bank.
如上所述，本發明的顏料分散液及包含其的著色光敏樹脂組合物的光學密度、黏度穩定性、表面粗糙度等物性優秀，不僅如此，可形成具有優秀的緊貼性的固化膜，從而可以有效地用於液晶顯示器用黑色矩陣、柱狀間隔物及黑色柱狀間隔物及有機發光二極體用黑堤等的製備。並且，從上述顏料分散液及包含其的著色光敏樹脂組合物製備的液晶顯示器及有機發光二極體等的顯示器件在顯影步驟之後，顯著減少在黑色圖案周圍的作為顏料分散液殘留物的殘渣，從而，與以往相比，具有卓越優秀的耐久性、壽命特性及可靠性。 As described above, the pigment dispersion liquid of the present invention and the colored photosensitive resin composition containing the same are excellent in physical properties such as optical density, viscosity stability, and surface roughness, and not only that, but also form a cured film with excellent adhesion, thereby It can be effectively used in the preparation of black matrixes, columnar spacers and black columnar spacers for liquid crystal displays, and black banks for organic light-emitting diodes. And, display devices such as liquid crystal displays and organic light-emitting diodes prepared from the above-mentioned pigment dispersion liquid and colored photosensitive resin composition containing the same, after the developing step, the residue as the pigment dispersion liquid residue around the black pattern is remarkably reduced. , Thus, compared with the past, it has excellent durability, life characteristics and reliability.
以下，藉由實施例更加詳細說明本發明。以下的實施例僅例示本發明，本發明的範圍並不局限於此。 Hereinafter, the present invention will be described in more detail by means of examples. The following examples merely illustrate the present invention, and the scope of the present invention is not limited thereto.
實施例 Example
黏結劑的製備 Binder preparation
製備例1 Preparation Example 1
向具備攪拌機、溫度計、回流冷卻管、滴液漏斗及氮導入管的內容積1.0L的圓燒瓶投入作為溶劑的122g的丙二醇單甲醚醋酸酯(PGMEA)及作為聚合引發劑的87g的1-甲氧基丙-2-醇(PGME)並進行攪拌。在此添加100g的苯硫基乙醇丙烯酸酯(PTEA)、101g的乙烯基甲苯單體(VTM)、80g的甲基丙烯酸四氫糠酯(THFMA)、74g的甲基丙烯酸(MAA)及61g的甲基丙烯酸苄酯(BzMA)之後，在90℃的溫度條件下反應17小時來獲取具有羧基的共聚物。上述反應在氮氣氛下執行。分析所製備的共聚物(黏結劑)的結果，酸值為65KOHmg/g，重均分子量為(Mw，GPC結果)12500g/mol，分散度為2.13。 122 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent and 87 g of 1- Methoxypropan-2-ol (PGME) and stirred. Add here 100 g of phenylthioethanol acrylate (PTEA), 101 g of vinyl toluene monomer (VTM), 80 g of tetrahydrofurfuryl methacrylate (THFMA), 74 g of methacrylic acid (MAA) and 61 g of After benzyl methacrylate (BzMA), the reaction was carried out at a temperature of 90° C. for 17 hours to obtain a copolymer having a carboxyl group. The above reaction was performed under nitrogen atmosphere. As a result of analyzing the prepared copolymer (binder), the acid value was 65KOHmg/g, the weight average molecular weight (Mw, GPC result) was 12500g/mol, and the degree of dispersion was 2.13.
所製備的上述共聚物(黏結劑)按1：3：1.5：3：1.6的莫耳比混合分別從甲基丙烯酸苄酯、甲基丙烯酸、苯硫基乙醇丙烯酸酯、乙烯基甲苯單體及甲基丙烯酸四氫糠酯衍生的重複單元。 The prepared above-mentioned copolymer (bonding agent) is mixed from benzyl methacrylate, methacrylic acid, phenylthioethanol acrylate, vinyl toluene monomer and Repeat unit derived from tetrahydrofurfuryl methacrylate.
製備例2 Preparation example 2
除將甲基丙烯酸的使用量變為94g，不使用甲基丙烯酸苄酯之外，藉由與上述製備例1相同的過程執行來製備共聚物(黏結劑)溶液。分析所製備的共聚物(黏結劑)的結果，酸值為67KOHmg/g，重均分子量為(Mw，GPC結果)12100g/mol，分散度為2.20。 A copolymer (binder) solution was prepared by performing the same procedure as in Preparation Example 1 above except that the amount of methacrylic acid used was changed to 94 g and benzyl methacrylate was not used. As a result of analyzing the prepared copolymer (binder), the acid value was 67KOHmg/g, the weight average molecular weight (Mw, GPC result) was 12100g/mol, and the degree of dispersion was 2.20.
所製備的共聚物(黏結劑)按1：0.5：1：1的莫耳比包含分別從甲基丙烯酸、苯硫基乙醇丙烯酸酯、甲基丙烯酸四氫糠酯衍生的重複單元。 The prepared copolymer (binder) contains repeating units derived from methacrylic acid, thiophenylethanol acrylate, and tetrahydrofurfuryl methacrylate, respectively, in a molar ratio of 1:0.5:1:1.
製備例3 Preparation example 3
向在製備例2中獲取的共聚物添加42g的甲基丙烯酸縮水甘油酯(GMA)，在氮氣氛下，在80℃的溫度條件下反應8小時來製備共聚物(黏結劑)溶液。分析所製備的共聚物(黏結劑)的結果，酸值為65KOHmg/g，重均分子量為(Mw，GPC結果)12000g/mol，分散度為2.11。 42 g of glycidyl methacrylate (GMA) was added to the copolymer obtained in Preparation Example 2, and reacted at 80° C. for 8 hours under a nitrogen atmosphere to prepare a copolymer (binder) solution. As a result of analyzing the prepared copolymer (binder), the acid value was 65KOHmg/g, the weight average molecular weight (Mw, GPC result) was 12000g/mol, and the degree of dispersion was 2.11.
所製備的上述共聚物(黏結劑)按1：3：1.5：3：1.6的比例包含分別從甲基丙烯酸縮水甘油酯、甲基丙烯酸、苯硫基乙醇丙烯酸酯、乙烯基甲苯單體及甲基丙烯酸四氫糠酯衍生的重複單元。 The prepared above-mentioned copolymer (binder) contains glycidyl methacrylate, methacrylic acid, phenylthioethanol acrylate, vinyl toluene monomer and formaldehyde in a ratio of 1:3:1.5:3:1.6. Repeating units derived from tetrahydrofurfuryl acrylate.
製備例4 Preparation Example 4
除將甲基丙烯酸及甲基丙烯酸縮水甘油酯的使用量分別變為81g及21g之外，藉由與上述製備例3相同的過程執行來製備共聚物(黏結劑)溶液。分析所製備的共聚物(黏結劑)的結果，酸值為63KOHmg/g，重均分子量為(Mw，GPC結果)115000g/mol，分散度為2.22。 A copolymer (binder) solution was prepared by performing the same procedure as in Preparation Example 3 above, except that the usage-amounts of methacrylic acid and glycidyl methacrylate were changed to 81 g and 21 g, respectively. As a result of analyzing the prepared copolymer (binder), the acid value was 63KOHmg/g, the weight average molecular weight (Mw, GPC result) was 115000g/mol, and the degree of dispersion was 2.22.
所製備的上述共聚物(黏結劑)按1：3：1.5：3：1.6的莫耳比包含分別從甲基丙烯酸縮水甘油酯、甲基丙烯酸、苯硫基乙醇丙烯酸酯、乙烯基甲苯單體及甲基丙烯酸四氫糠酯衍生的重複單元。 The prepared above-mentioned copolymer (bonding agent) contains glycidyl methacrylate, methacrylic acid, phenylthioethanol acrylate, vinyl toluene monomers at a molar ratio of 1:3:1.5:3:1.6 and repeating units derived from tetrahydrofurfuryl methacrylate.
實施例1 Example 1
(1)顏料分散液的製備 (1) Preparation of pigment dispersion
(步驟1)預混合(pre-mixing)過程 (Step 1) Pre-mixing process
以100重量份的顏料(BASF公司Black 582)為基準，混合150重量份的丙二醇單甲醚(PGME)、80重量份的分散劑(BYK公司Disperbyk-2001)、80重量份的在上述製備例1中製備的黏結劑及1重量份的分散助劑(Solsperse 22000)之後，在1000rpm下預混合60分鐘來製備原料混合物。 Based on 100 parts by weight of pigment (BASF company Black 582), mix 150 parts by weight of propylene glycol monomethyl ether (PGME), 80 parts by weight of dispersant (BYK company Disperbyk-2001), 80 parts by weight of the above-mentioned preparation example The binder prepared in 1 and 1 part by weight of a dispersing aid (Solsperse 22000) were pre-mixed at 1000 rpm for 60 minutes to prepare a raw material mixture.
(步驟2)第一次分散過程 (Step 2) First Dispersion Process
利用0.5mm至1.2mm的比較大的珠來對在上述步驟1中製備的原料混合物進行第一次研磨，由此，將原料混合物內的巨大凝集粒子均質化。 The raw material mixture prepared in the above-mentioned step 1 is ground for the first time using relatively large beads of 0.5 mm to 1.2 mm, thereby homogenizing the giant aggregated particles in the raw material mixture.
(步驟3)第二次分散過程 (Step 3) second dispersion process
利用0.3mm至0.05mm的微小珠來對在上述步驟2中獲取的第一次研磨的原料混合物進行第二次研磨，由此可以將原料混合物內的粒子微細化(設備：油漆振動器)。 The first milled raw material mixture obtained in the above-mentioned step 2 is subjected to second grinding using microbeads of 0.3 mm to 0.05 mm, whereby particles in the raw material mixture can be miniaturized (equipment: paint vibrator).
(步驟4)分散穩定化過程 (Step 4) Dispersion Stabilization Process
在常溫條件下將在上述步驟3中獲取的第二次研磨的原料混合物熟成36小時來製備需要的顏料分散液。 The second grinding raw material mixture obtained in the above step 3 was matured for 36 hours at room temperature to prepare the required pigment dispersion.
(2)著色光敏樹脂組合物的製備 (2) Preparation of colored photosensitive resin composition
攪拌上述顏料分散液，以固體成分含量為基準，在42重量百分比的對應顏料分散液添加6重量百分比的光聚合化合物、1重量百分比的光聚合引發劑、0.4重量百分比的添加劑(均染劑)及50.6重量百分比的溶劑，在8℃的溫度條件下執行3小時以上的穩定化過程來製備需要的著色光敏樹脂組合物。 Stir the above-mentioned pigment dispersion, based on the solid content, add 6% by weight of photopolymerization compound, 1% by weight of photopolymerization initiator, and 0.4% by weight of additive (leveling agent) to the corresponding pigment dispersion of 42% by weight and 50.6% by weight of the solvent, and perform a stabilization process for more than 3 hours at a temperature of 8° C. to prepare the desired colored photosensitive resin composition.
在此情況下，作為光聚合化合物，使用二季戊四醇六丙烯酸酯(DPHA，美院商社(株))，作為光聚合引發劑，使用OXE-02(IRGACURE公司)，作為添加劑，使用DIC F-554(DIC KOREA)，作為溶劑，使用丙二醇單甲醚醋酸酯(PGMEA)。 In this case, dipentaerythritol hexaacrylate (DPHA, Meiyuan Trading Co., Ltd.) was used as the photopolymerization compound, OXE-02 (IRGACURE Co., Ltd.) was used as the photopolymerization initiator, and DIC F-554 was used as the additive. (DIC KOREA) used propylene glycol monomethyl ether acetate (PGMEA) as a solvent.
實施例2 Example 2
除代替在製備例1中製備的黏結劑，使用在製備例2中製備的黏結劑之外，執行與上述實施例1相同的過程來製備顏料分散液及著色光敏樹脂組合物。 Except that the binder prepared in Preparation Example 2 was used instead of the binder prepared in Preparation Example 1, the same process as in Example 1 above was performed to prepare a pigment dispersion and a colored photosensitive resin composition.
比較例1 Comparative example 1
除代替在製備例1中製備的黏結劑，使用在製備例3中製備的黏結劑之外，執行與上述實施例1相同的過程來製備顏料分散液及著色光敏樹脂組合物。 Except that the binder prepared in Preparation Example 3 was used instead of the binder prepared in Preparation Example 1, the same process as in Example 1 above was performed to prepare a pigment dispersion and a colored photosensitive resin composition.
比較例2 Comparative example 2
除代替在製備例1中製備的黏結劑，使用在製備例3中製備的黏結劑之外，執行與上述實施例1相同的過程來製備顏料分散液及著色光敏樹脂組合物。 Except that the binder prepared in Preparation Example 3 was used instead of the binder prepared in Preparation Example 1, the same process as in Example 1 above was performed to prepare a pigment dispersion and a colored photosensitive resin composition.
比較例3 Comparative example 3
除代替在製備例1中製備的黏結劑，使用市場銷售的黏結劑(SPCO-823X，昭和電工)之外，執行與上述實施例1相同的過程來製備顏料分散液及著色光敏樹脂組合物。 Except for using a commercially available binder (SPCO-823X, Showa Denko) instead of the binder prepared in Preparation Example 1, the same process as in Example 1 above was performed to prepare a pigment dispersion and a colored photosensitive resin composition.
<試驗例> <Test example>
試驗例1：光學密度 Test Example 1: Optical Density
利用旋塗來分別將在上述實施例及比較例中製備的著色光敏樹脂組合物塗敷在玻璃基板上之後，在95℃的溫度條件下進行固化來形成厚度為1μm的塗膜。使用X-Rite公司的361T比重計(densitometer)來測定上述塗膜的光學密度(OD)。 The colored photosensitive resin compositions prepared in the above examples and comparative examples were coated on glass substrates by spin coating, and then cured at a temperature of 95° C. to form coating films with a thickness of 1 μm. The optical density (OD) of the said coating film was measured using the 361T densitometer (densitometer) of X-Rite company.
試驗例2：表面電阻 Test Example 2: Surface Resistance
使用Mitsubishi Chemical Analytech公司的Hiresta-ux(MCP-HT800)來測定在上述試驗例1中製備的塗膜表面的表面電阻。 The surface resistance of the surface of the coating film prepared in Test Example 1 above was measured using Hiresta-ux (MCP-HT800) of Mitsubishi Chemical Analytech Corporation.
試驗例3：粒徑 Test Example 3: Particle Size
將在上述實施例及比較例中獲取的光敏樹脂組合物在丙二醇單甲醚醋酸酯溶劑稀釋100倍之後，使用Horiba公司的LB-550測定設備來測定10次粒徑並求出平均粒徑。 After diluting the photosensitive resin composition obtained in the above-mentioned examples and comparative examples 100 times with propylene glycol monomethyl ether acetate solvent, the particle size was measured 10 times using Horiba's LB-550 measuring device to obtain the average particle size.
試驗例4：表面粗糙度 Test Example 4: Surface Roughness
藉由Keynece公司的VHX-1000E光學顯微鏡3000倍率觀察在上述試驗例1中製備的塗膜的表面來評價表面粗糙度。在此情況下，塗膜的厚度以2.4μm為基準。 Surface roughness was evaluated by observing the surface of the coating film prepared in the above-mentioned Test Example 1 with a VHX-1000E optical microscope of Keynece Corporation at a magnification of 3000. In this case, the thickness of the coating film is based on 2.4 μm.
表面粗糙度的評價基準如下： The evaluation criteria of surface roughness are as follows:
○：光滑的表面 ○: smooth surface
△：多少粗糙的表面 △: How rough the surface is
X：粗糙的表面 X: rough surface
試驗例5：緊貼性 Test Example 5: Adherence
利用旋塗來在玻璃基板上分別塗敷在上述實施例及比較例中製備的著色光敏樹脂組合物之後，在95℃的溫度條件下熱處理1分鐘來固化並形成厚度為2.4μm的塗膜。接著，在塗膜適用光罩並在汞燈下照射50mJ/cm2的能量。在常溫條件下，使用0.05重量百分比的KOH水溶液來以噴霧法顯影完成曝光的塗膜之後藉由蒸餾水進行洗滌。藉由Keynece公司的VHX-1000E光學顯微鏡200倍率觀察在玻璃基板剩留的微細圖案(圖案線寬：1~40μm)來測定剩餘的最小微細圖案大小。 After coating the colored photosensitive resin compositions prepared in the above examples and comparative examples on the glass substrate by spin coating, heat treatment was performed at 95° C. for 1 minute to cure and form a coating film with a thickness of 2.4 μm. Next, apply a photomask to the coating film and irradiate energy of 50 mJ/cm 2 under a mercury lamp. Under normal temperature conditions, 0.05% by weight of KOH aqueous solution was used to develop the exposed coating film by spray method and then washed with distilled water. The size of the remaining minimum fine pattern was determined by observing the remaining fine pattern (pattern line width: 1-40 μm) on the glass substrate with a VHX-1000E optical microscope from Keynece Company at a magnification of 200.
試驗例6：殘渣 Test Example 6: Residue
利用電子掃描顯微鏡(SEM)評價了在黑色圖案周圍的顏料分散液的殘留物(殘渣)是否殘留。 Whether or not the residue (residue) of the pigment dispersion liquid remained around the black pattern was evaluated using a scanning electron microscope (SEM).
殘渣的評價基準考慮到殘渣的數量和大小如下確定： The evaluation criteria for residues are determined as follows taking into account the amount and size of residues:
○：剩留小於10%的殘留固體成分 ○: Less than 10% residual solid content remains
△：剩留10%以上至90%以下的殘留固體成分 △: More than 10% to less than 90% of residual solid content remains
X：剩留90%以上至100%以下的殘留固體成分 X: More than 90% to less than 100% of the residual solid content remains
試驗例7：顏料分散液的黏度及穩定性 Test Example 7: Viscosity and Stability of Pigment Dispersion
利用布魯克菲爾德黏度計(Brookfield Viscometer)來測定在實施例及比較例中製備的顏料分散液在25℃溫度條件下的初始黏度及在25℃的溫度條件下維持7日時的黏度變化率並評價了穩定性。 Utilize the Brookfield Viscometer (Brookfield Viscometer) to measure the initial viscosity of the pigment dispersion liquid prepared in the embodiment and the comparative example under the temperature condition of 25 ℃ and the viscosity change rate when maintaining 7 days under the temperature condition of 25 ℃ and evaluate stability.
從上述表的實驗結果，與比較例相比，具有包含特定單體的共聚物的丙烯酸樹脂的實施例的顏料分散液及從此製備的塗膜在光學密度及初始黏度等方面呈現出相同水平的物性，並呈現出優秀的圖案粗糙度及黏度穩定性並呈現出得到改善的殘渣結果。 From the experimental results in the above table, compared with the comparative example, the pigment dispersion liquid of the example having the acrylic resin containing the copolymer of the specific monomer and the coating film prepared therefrom showed the same level of optical density and initial viscosity. physical properties, and exhibited excellent pattern roughness and viscosity stability, and exhibited improved residue results.
具體地，與利用使用甲基丙烯酸縮水甘油酯的製備例3及製備例4的顏料分散液的情況相比，在利用不使用甲基丙烯酸縮水甘油酯的製備例1及製備例2的顏料分散液的實施例1及實施例2的情況下，在黑色圖案周圍的顏料分散液的殘留物(殘渣)尤其顯著減少。 Specifically, compared with the case of using the pigment dispersions of Preparation Example 3 and Preparation Example 4 using glycidyl methacrylate, the pigment dispersions of Preparation Example 1 and Preparation Example 2 that did not use glycidyl methacrylate In the case of Example 1 and Example 2, the residue (residue) of the pigment dispersion liquid around the black pattern was significantly reduced.
尤其，不使用甲基丙烯酸縮水甘油酯，而是利用使用甲基丙烯酸苄酯、甲基丙烯酸、苯硫基乙醇丙烯酸酯、乙烯基甲苯單體及甲基丙烯酸 四氫糠酯的單體的製備例1的顏料分散液的實施例1的情況下，黑色圖案周圍的殘渣改善效果優秀，不僅如此，在常溫條件下維持7日時，黏度的變化率，即，黏度穩定性方面也呈現出優秀的結果，圖案粗糙度、光學特性、緊貼性等方面均呈現出優秀的結果。 In particular, instead of using glycidyl methacrylate, benzyl methacrylate, methacrylic acid, phenylthioethanol acrylate, vinyl toluene monomer and methacrylic acid In the case of Example 1 of the pigment dispersion liquid of Preparation Example 1 of Tetrahydrofurfuryl Monomer, the effect of improving the residue around the black pattern was excellent, and not only that, but also the rate of change in viscosity when maintained at room temperature for 7 days, that is, It also showed excellent results in terms of viscosity stability, and excellent results in terms of pattern roughness, optical properties, and adhesion.
相反，不使用甲基丙烯酸苄酯，在利用使用甲基丙烯酸縮水甘油酯的製備例3及製備例4的顏料分散液的比較例1和比較例2的情況下，黏度穩定性及圖案粗糙度優秀，但在黑色圖案周圍的殘渣顯著增加。 On the contrary, in the case of Comparative Example 1 and Comparative Example 2 using the pigment dispersion liquids of Preparation Example 3 and Preparation Example 4 using glycidyl methacrylate without using benzyl methacrylate, the viscosity stability and pattern roughness Excellent, but significantly increased residue around black patterns.
並且，在使用市場銷售的黏結劑(SPCO-823X，昭和電工)的比較例3的情況下，圖案粗糙度及常溫穩定性方面惡劣，在黑色圖案周圍的殘渣顯著增加。 In addition, in the case of Comparative Example 3 using a commercially available adhesive (SPCO-823X, Showa Denko), the pattern roughness and room temperature stability were poor, and residues around the black pattern significantly increased.
有關上述殘渣改善效果，參照圖1，與使用比較例2及比較例3的顏料分散液的情況相比，在使用實施例1的顏料分散液的情況下，黑色圖案周圍的顏料分散液的殘留物(殘渣)顯著減少。 With reference to Fig. 1 regarding the above-mentioned residue improvement effect, compared with the cases of using the pigment dispersion liquids of Comparative Examples 2 and 3, in the case of using the pigment dispersion liquid of Example 1, the residue of the pigment dispersion liquid around the black pattern was reduced. Substances (residue) are significantly reduced.
因此，利用本發明實例的顏料分散液的實施例1及實施例2在表面粗糙度、黏度穩定性及黑色圖案周圍的殘渣結果方面均呈現出得到改善的效果。 Therefore, both Example 1 and Example 2 using the pigment dispersion of the present invention showed improved effects in terms of surface roughness, viscosity stability, and residue around the black pattern.
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| KR20220071428A (en) | 2022-05-31 |
| TW202221051A (en) | 2022-06-01 |
| CN114539850B (en) | 2023-08-04 |
| CN114539850A (en) | 2022-05-27 |
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