JP5445359B2 - Red coloring composition for color filter and color filter - Google Patents
Red coloring composition for color filter and color filter Download PDFInfo
- Publication number
- JP5445359B2 JP5445359B2 JP2010152680A JP2010152680A JP5445359B2 JP 5445359 B2 JP5445359 B2 JP 5445359B2 JP 2010152680 A JP2010152680 A JP 2010152680A JP 2010152680 A JP2010152680 A JP 2010152680A JP 5445359 B2 JP5445359 B2 JP 5445359B2
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- pigment
- formula
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- carbon atoms
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 68
- 238000004040 coloring Methods 0.000 title claims description 45
- 239000000049 pigment Substances 0.000 claims description 145
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 claims description 27
- 125000001424 substituent group Chemical group 0.000 claims description 25
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 23
- 150000004056 anthraquinones Chemical class 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 12
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
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- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
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- 125000005650 substituted phenylene group Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
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- -1 polyazo Polymers 0.000 description 26
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 15
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- 239000001054 red pigment Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 9
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- 238000006243 chemical reaction Methods 0.000 description 7
- 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 6
- FZEYVTFCMJSGMP-UHFFFAOYSA-N acridone Chemical class C1=CC=C2C(=O)C3=CC=CC=C3NC2=C1 FZEYVTFCMJSGMP-UHFFFAOYSA-N 0.000 description 6
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- 238000002360 preparation method Methods 0.000 description 6
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- 239000000126 substance Substances 0.000 description 5
- 239000001052 yellow pigment Substances 0.000 description 5
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- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- GDALETGZDYOOGB-UHFFFAOYSA-N Acridone Natural products C1=C(O)C=C2N(C)C3=CC=CC=C3C(=O)C2=C1O GDALETGZDYOOGB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012860 organic pigment Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
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- 238000002834 transmittance Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PVMCQBPJKPMOKM-UHFFFAOYSA-N 1-cyclopentylpiperazine Chemical compound C1CCCC1N1CCNCC1 PVMCQBPJKPMOKM-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- 125000003277 amino group Chemical group 0.000 description 2
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- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
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Landscapes
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
Description
本発明は、カラー液晶表示装置、カラー撮像管素子等に用いられるカラーフィルタの製造に使用されるカラーフィルタ用赤色着色組成物、およびこれを用いて形成されるカラーフィルタに関する。 The present invention relates to a red coloring composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter formed using the same.
近年、テレビモニタ用途で液晶表示装置が応用されており、カラーフィルタに対しては、透過度、すなわち明度や色純度、さらに画素を形成する際の塗布均一性、感度、現像性、パターン形状など、各種特性に対する要求レベルが高まってきている。この中でも、低消費電力のパネルを作製するためには明るいカラーフィルタが必要となり、明度の向上という要求特性が重要視されてきている。
カラーフィルタの色特性、明度の向上を図るために、従来は赤色着色組成物を赤色顔料と黄色顔料で調色する方法が採用されてきた。しかし、上記の要求特性に加え、さらにカラーフィルタの色再現領域の拡大、薄膜化を図ろうとする場合、赤色顔料1種類と黄色顔料1種類による調色には限界があった。
In recent years, liquid crystal display devices have been applied to TV monitor applications. For color filters, the transmittance, that is, the lightness and color purity, coating uniformity when forming pixels, sensitivity, developability, pattern shape, etc. Demand levels for various characteristics are increasing. Among these, a bright color filter is required to produce a panel with low power consumption, and the required characteristic of improving brightness has been regarded as important.
In order to improve the color characteristics and brightness of the color filter, conventionally, a method of toning a red coloring composition with a red pigment and a yellow pigment has been employed. However, in addition to the above required characteristics, when trying to expand the color reproduction region of the color filter and reduce the film thickness, there is a limit to the color matching with one type of red pigment and one type of yellow pigment.
本発明の目的は、色特性に優れたカラーフィルタ用着色組成物、および色特性に優れかつ薄膜なカラーフィルタを提供することである。 The objective of this invention is providing the coloring composition for color filters excellent in the color characteristic, and the color filter excellent in a color characteristic, and a thin film.
本発明のカラーフィルタ用赤色着色組成物は、透明樹脂、その前駆体またはそれらの混合物からなる顔料担体と、下記一般式(1)または(2)で表されるアントラキノン系顔料と、下記一般式(3)で表されるジケトピロロピロール系顔料と、下記式(7)の塩基性基を有するアントラキノン系顔料誘導体と、下記式(4)の塩基性基、下記式(5)の塩基性基、下記式(6)の塩基性基および下記式(7)の塩基性基からなる群より選ばれる少なくとも1つの塩基性基を有するジケトピロロピロール系顔料誘導体とを含むことを特徴とする。
式(1)
式(2)
式(3)
(上記式(1)、(2)において、Aは、それぞれ独立に、水素原子または置換基を有してもよいアルキル基もしくはアリール基を表す。上記式(3)において、Bは、それぞれ独立に、水素原子、置換されてもよい飽和もしくは不飽和のアルキル基、シアノ基、置換されてもよいアリール基、またはハロゲン原子を示す。)
式(4)
式(8)
式(9)
また、本発明のカラーフィルタは、上記赤色着色組成物から形成されるフィルタセグメントを具備することを特徴とする。
The red coloring composition for a color filter of the present invention comprises a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, an anthraquinone pigment represented by the following general formula (1) or (2), and the following general formula: (3) and the diketopyrrolopyrrole pigment represented by the luer Ntorakinon pigment derivative having a basic group under following formula (7), a basic group of the formula (4), the following equation (5 ), A diketopyrrolopyrrole pigment derivative having at least one basic group selected from the group consisting of a basic group of the following formula (6) and a basic group of the following formula (7). It is characterized by.
Formula (1)
Formula (2)
Formula (3)
(In the above formulas (1) and (2), A each independently represents a hydrogen atom or an alkyl group or aryl group which may have a substituent. In the above formula (3), B represents each independently. Represents a hydrogen atom, a saturated or unsaturated alkyl group which may be substituted, a cyano group, an aryl group which may be substituted, or a halogen atom.)
Formula (4)
Formula (8)
Formula (9)
Moreover, the color filter of this invention comprises the filter segment formed from the said red coloring composition.
本発明のカラーフィルタ用赤色着色組成物は、特定の2種類の赤色顔料と、塩基性基を有するアントラキノン系顔料誘導体と、塩基性基を有するジケトピロロピロール系顔料誘導体とを含むため、分光特性が効率良く調整されており、該赤色着色組成物を用いて赤色フィルタセグメントを形成することによりカラーフィルタの薄膜化を達成することができる。 Since the red coloring composition for a color filter of the present invention contains two specific types of red pigment, an anthraquinone pigment derivative having a basic group, and a diketopyrrolopyrrole pigment derivative having a basic group, The characteristics are adjusted efficiently, and it is possible to reduce the thickness of the color filter by forming a red filter segment using the red coloring composition.
まず、本発明のカラーフィルタ用赤色着色組成物について説明する。
本発明のカラーフィルタ用赤色着色組成物は、透明樹脂、その前駆体またはそれらの混合物からなる顔料担体と、一般式(1)または(2)で表されるアントラキノン系顔料と、一般式(3)で表されるジケトピロロピロール系顔料と、下記式(7)の塩基性基を有するアントラキノン系顔料誘導体と、下記式(4)の塩基性基、下記式(5)の塩基性基、下記式(6)の塩基性基および下記式(7)の塩基性基からなる群より選ばれる少なくとも1つの塩基性基を有するジケトピロロピロール系顔料誘導体とを含むことを特徴とする。特定の2種の赤色顔料を組み合わせる理由は、各顔料が持っている透過スペクトルを有効的に合わせ、最大限性能を発揮させるためである。特定の2種の赤色顔料を組み合わせることにより、分光スペクトルの透過領域が広げ、同時に同系色の顔料を用いるため、赤色着色組成物としての濃度が濃く、従来よりも薄膜なカラーフィルタを得ることができる。
First, the red coloring composition for color filters of the present invention will be described.
The red coloring composition for a color filter of the present invention comprises a pigment carrier comprising a transparent resin, a precursor thereof, or a mixture thereof, an anthraquinone pigment represented by the general formula (1) or (2), and a general formula (3 a diketopyrrolopyrrole pigment represented by), and a luer Ntorakinon pigment derivative having a basic group under following formula (7), a basic group of the formula (4), the following formula (5) And a diketopyrrolopyrrole pigment derivative having at least one basic group selected from the group consisting of a basic group, a basic group of the following formula (6), and a basic group of the following formula (7). And The reason for combining two specific red pigments is to effectively match the transmission spectrum of each pigment and to maximize performance. By combining two specific types of red pigments, the spectral spectrum transmission region is expanded, and at the same time, pigments of the same color are used, so that a color filter having a higher concentration as a red coloring composition and a thinner film than before can be obtained. it can.
一般式(1)または(2)で表されるアントラキノン系顔料としては、C.I.Pigment Red 89、177等が挙げられるが、色相、分光特性の点からC.I.Pigment Red 177が好ましい。
一般式(3)で表されるジケトピロロピロール系顔料としては、C.I.Pigment Red 254、264等が挙げられるが、色相、分光特性の点からC.I.Pigment Red 254が好ましい。
Examples of the anthraquinone pigment represented by the general formula (1) or (2) include C.I. I. Pigment Red 89, 177 and the like, but C.I. I. Pigment Red 177 is preferred.
Examples of the diketopyrrolopyrrole pigment represented by the general formula (3) include C.I. I. Pigment Red 254, 264 and the like, but C.I. I. Pigment Red 254 is preferred.
一般式(1)または(2)で表されるアントラキノン系顔料と一般式(3)で表されるジケトピロロピロール系顔料は、重量比で好ましくは1:99〜40:60、より好ましくは1:99〜30:70の割合で含有される。一般式(1)または(2)で表されるアントラキノン系の配合量が上記範囲よりも多いと、アントラキノン系顔料の分光特性により充分に明度が上がらず、逆に上記範囲よりも少なければ、ジケトピロロピロール系顔料の分光特性により黄味が強くなり、目標の色度(x、y)からのずれが大きくなってしまう。 The anthraquinone pigment represented by the general formula (1) or (2) and the diketopyrrolopyrrole pigment represented by the general formula (3) are preferably 1:99 to 40:60, more preferably, by weight ratio. It is contained in a ratio of 1:99 to 30:70. If the amount of the anthraquinone-based compound represented by the general formula (1) or (2) is larger than the above range, the brightness will not be sufficiently increased due to the spectral characteristics of the anthraquinone-based pigment. Due to the spectral characteristics of the ketopyrrolopyrrole pigment, yellowishness becomes strong, and deviation from the target chromaticity (x, y) becomes large.
本発明のカラーフィルタ用赤色着色組成物には、C.I.Pigment Red 7、14、41、48:1、48:2、48:3、48:4、81:1、81:2、81:3、81:4、146、184、185、187、200、202、208、210、246、255、270、272、279等の赤色顔料、C.I.Pigment Orange 36、43、51、55、59、61、71、73等の橙色顔料を併用することができる。
また、色度調色のために、C.I.Pigment Yellow 1、2、3、4、5、6、10、12、13、14、15、16、17、18、24、31、32、34、35、35:1、36、36:1、37、37:1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、126、127、128、129、138、139、147、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、198、199、213、214等の黄色顔料を併用することができる。
この場合、顔料の全量(本発明のアントラキノン系顔料、ジケトピロロピロール系顔料、その他の赤色顔料、橙色顔料と黄色顔料の合計量)を基準とする本発明のアントラキノン系顔料とジケトピロロピロール系顔料の含有量は、要求される色特性に応じて異なるが、充分な明度を得る観点から60〜100重量%、特に90〜99重量%であることが好ましい。
The red coloring composition for color filters of the present invention includes C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 184, 185, 187, 200, Red pigments such as 202, 208, 210, 246, 255, 270, 272, and 279; I. Orange pigments such as Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 can be used in combination.
For chromaticity toning, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 It can be used in combination with the yellow pigments such as 181,182,185,187,188,193,194,198,199,213,214.
In this case, the anthraquinone pigment of the present invention and the diketopyrrolopyrrole based on the total amount of the pigment (the total amount of the anthraquinone pigment, diketopyrrolopyrrole pigment, other red pigment, orange pigment and yellow pigment of the present invention). The content of the system pigment varies depending on the required color characteristics, but is preferably 60 to 100% by weight, particularly 90 to 99% by weight from the viewpoint of obtaining sufficient brightness.
本発明のカラーフィルタ用赤色着色組成物には、彩度と明度のバランスをとりつつ良好な塗布性、感度、現像性等を確保するため、酸化チタン、硫酸バリウム、亜鉛華、硫酸鉛、黄色鉛、亜鉛黄、べんがら(赤色酸化鉄(III))、カドミウム赤、群青、紺青、酸化クロム緑、コバルト緑、アンバー、チタンブラック、合成鉄黒、カーボンブラック等の無機顔料を含有させることができる。
本発明のカラーフィルタ用赤色着色組成物は、本発明のアントラキノン系顔料、ジケトピロロピロール系顔料を含む数種類の顔料を混合した後、得られた顔料混合物を顔料担体中に既知の方法で微細に分散して製造することができる。また、赤色着色組成物は、各々の顔料を別々に顔料担体中に微細に分散したものを混合して製造することもできる。
The red coloring composition for a color filter of the present invention has titanium oxide, barium sulfate, zinc white, lead sulfate, yellow in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness. Inorganic pigments such as lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black can be included. .
The red coloring composition for a color filter of the present invention is prepared by mixing several kinds of pigments including the anthraquinone pigment and diketopyrrolopyrrole pigment of the present invention, and finely mixing the resulting pigment mixture in a pigment carrier by a known method. It can be dispersed and manufactured. The red coloring composition can also be produced by mixing each pigment separately finely dispersed in a pigment carrier.
本発明のカラーフィルタ用赤色着色組成物においては、顔料の凝集を防ぎ、顔料が微細に分散した状態を維持し、良好な流動性と安定性を併せ持ち、さらに膜厚均一性に優れた赤色着色組成物を得るため、アントラキノン系顔料誘導体およびジケトピロロピロール系顔料誘導体であって、下記式(4)の塩基性基、式(5)の塩基性基、式(6)の塩基性基および式(7)の塩基性から選ばれる少なくとも1つの塩基性基(以下、「特定の塩基性基」ということがある)を有するものを含む。さらに、その他の顔料誘導体、アントラキノン誘導体、アクリドン誘導体またはジケトピロロピロール誘導体から選ばれる少なくとも一種の誘導体であって、下記式(4)の塩基性基、式(5)の塩基性基、式(6)の塩基性基および式(7)の塩基性から選ばれる少なくとも1つの塩基性基(以下、「特定の塩基性基」ということがある)を有するものを含有させることもできる。 In the red coloring composition for a color filter of the present invention, the pigment is prevented from agglomerating, the pigment is kept in a finely dispersed state, has both good fluidity and stability, and has excellent film thickness uniformity. In order to obtain a composition, an anthraquinone pigment derivative and a diketopyrrolopyrrole pigment derivative, which are a basic group of the following formula (4), a basic group of the formula (5), a basic group of the formula (6), and Those having at least one basic group selected from the basicity of formula (7) (hereinafter sometimes referred to as “specific basic group”) are included. Furthermore, it is at least one derivative selected from other pigment derivatives, anthraquinone derivatives, acridone derivatives or diketopyrrolopyrrole derivatives, and includes a basic group of the following formula (4), a basic group of the formula (5), a formula ( Those having at least one basic group selected from the basic group of 6) and the basic group of formula (7) (hereinafter sometimes referred to as “specific basic group”) may also be included.
式(4)
式(8)
Formula (8)
本発明のカラーフィルタ用赤色着色組成物に用いるアントラキノン系顔料に対して用いる顔料誘導体は、アントラキノン骨格を有するものが、顔料分散体の流動性とその安定性の面から特に好ましい。また、ジケトピロロピロール系顔料に対して用いる顔料誘導体は、ジケトピロロピロール骨格を有するものが、顔料分散体の流動性とその安定性の面から特に好ましい。
上記特定の塩基性基を有する誘導体の含有量は、顔料を基準として、好ましくは0.001〜40重量%、さらに好ましくは1〜20重量%である。
The pigment derivative used for the anthraquinone pigment used in the red coloring composition for a color filter of the present invention is particularly preferably one having an anthraquinone skeleton from the viewpoint of the fluidity and stability of the pigment dispersion. Further, the pigment derivative used for the diketopyrrolopyrrole pigment preferably has a diketopyrrolopyrrole skeleton from the viewpoint of the fluidity and stability of the pigment dispersion.
The content of the derivative having the specific basic group is preferably 0.001 to 40% by weight, more preferably 1 to 20% by weight, based on the pigment.
特定の塩基性基を有する顔料誘導体を構成する有機顔料としては、例えば、ジケトピロロピロール系顔料、アゾ、ジスアゾ、ポリアゾ等のアゾ系顔料、フタロシアニン系顔料、ジアミノジアントラキノン、アントラピリミジン、フラバントロン、アントアントロン、インダントロン、ピラントロン、ビオラントロン等のアントラキノン系顔料、キナクリドン系顔料、ジオキサジン系顔料、ペリノン系顔料、ペリレン系顔料、チオインジゴ系顔料、イソインドリン系顔料、イソインドリノン系顔料、キノフタロン系顔料、スレン系顔料、金属錯体系顔料が挙げられる。また、先に示した本発明の赤色着色組成物に用いられる顔料でもよい。 Examples of the organic pigment constituting the pigment derivative having a specific basic group include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo, phthalocyanine pigments, diaminodianthraquinone, anthrapyrimidine, and flavantrons. Anthraquinone pigments such as anthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindolinone pigment, quinophthalone pigment Selenium pigments and metal complex pigments. Moreover, the pigment used for the red coloring composition of this invention shown previously may be sufficient.
また、特定の塩基性基を有するアントラキノン誘導体および特定の塩基性基を有するアクリドン誘導体を構成するアントラキノンおよびアクリドンは、メチル基、エチル基等のアルキル基、アミノ基、ニトロ基、水酸基、またはメトキシ基、エトキシ基等のアルコキシ基、または塩素等のハロゲン等の置換基を有していてもよいアントラキノンおよびアクリドンである。
また、特定の塩基性基を有するジケトピロロピロール誘導体を構成するジケトピロロピロールは、置換されてもよい飽和もしくは不飽和のアルキル基、シアノ基、置換されてもよいアリール基、ハロゲン基等の置換基を有していてもよいジケトピロロピロールである。
Anthraquinone and acridone constituting an anthraquinone derivative having a specific basic group and an acridone derivative having a specific basic group are an alkyl group such as a methyl group, an ethyl group, an amino group, a nitro group, a hydroxyl group, or a methoxy group. Anthraquinone and acridone which may have a substituent such as an alkoxy group such as ethoxy group or a halogen such as chlorine.
In addition, diketopyrrolopyrrole constituting a diketopyrrolopyrrole derivative having a specific basic group is a saturated or unsaturated alkyl group that may be substituted, a cyano group, an aryl group that may be substituted, a halogen group, etc. It is diketopyrrolopyrrole which may have the following substituents.
特定の塩基性基を有する顔料誘導体、アントラキノン誘導体およびアクリドン誘導体は、種々の合成経路で合成することができる。例えば、有機顔料、アントラキノンまたはアクリドンに、下記式(11)〜(14)で表される置換基を導入した後、該置換基と反応して一般式(4)〜(7)で表される置換基を形成するアミン成分、例えば、N,N−ジメチルアミノプロピルアミン、N−メチルピペラジン、ジエチルアミンまたは4−[4−ヒドロキシ−6−[3−(ジブチルアミノ)プロピルアミノ]−1,3,5−トリアジン−2−イルアミノ]アニリン等を反応させることによって得られる。 Pigment derivatives, anthraquinone derivatives and acridone derivatives having a specific basic group can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the following formulas (11) to (14) into an organic pigment, anthraquinone or acridone, it reacts with the substituent and is represented by general formulas (4) to (7). Amine components that form substituents such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3 It can be obtained by reacting 5-triazin-2-ylamino] aniline or the like.
式(11) −SO2Cl
式(12) −COCl
式(13) −CH2NHCOCH2Cl
式(14) −CH2Cl
有機顔料がアゾ系顔料である場合は、一般式(4)〜(7)で表される置換基をあらかじめジアゾ成分またはカップリング成分に導入し、その後カップリング反応を行うことによって塩基性基を有するアゾ系顔料誘導体を製造することもできる。
Formula (11) -SO 2 Cl
Formula (12) -COCl
Equation (13) -CH 2 NHCOCH 2 Cl
Equation (14) -CH 2 Cl
When the organic pigment is an azo pigment, the basic group is introduced by introducing the substituent represented by the general formulas (4) to (7) into the diazo component or the coupling component in advance and then performing a coupling reaction. An azo pigment derivative having the same can also be produced.
また、特定の塩基性基を有するジケトピロロピロール誘導体も、種々の合成経路で合成することができる。例えば、塩化シアヌルを出発原料とし、塩化シアヌルの少なくとも1つの塩素に一般式(4)〜(7)で表される置換基を形成するアミン成分、例えば、N,N−ジメチルアミノプロピルアミンまたはN−メチルピペラジン等を反応させ、次いで塩化シアヌルの残りの塩素と種々のアミンまたはアルコール等を反応させることによって得られる。 In addition, diketopyrrolopyrrole derivatives having a specific basic group can also be synthesized by various synthetic routes. For example, an amine component starting from cyanuric chloride and forming a substituent represented by the general formulas (4) to (7) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N It is obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.
特定の塩基性基を形成するために使用されるアミン成分としては、例えば、ジメチルアミン、ジエチルアミン、N,N−エチルイソプロピルアミン、N,N−エチルプロピルアミン、N,N−メチルブチルアミン、N,N−メチルイソブチルアミン、N,N−ブチルエチルアミン、N,N−tert−ブチルエチルアミン、ジイソプロピルアミン、ジプロピルアミン、N,N−sec−ブチルプロピルアミン、ジブチルアミン、ジーsec−ブチルアミン、ジイソブチルアミン、N,N−イソブチル−sec−ブチルアミン、ジアミルアミン、ジイソアミルアミン、ジヘキシルアミン、ジ(2−エチルへキシル)アミン、ジオクチルアミン、N,N−メチルオクタデシルアミン、ジデシルアミン、ジアリルアミン、N,N−エチル−1,2−ジメチルプロピルアミン、N,N−メチルヘキシルアミン、ジオレイルアミン、ジステアリルアミン、N,N−ジメチルアミノメチルアミン、N,N−ジメチルアミノエチルアミン、N,N−ジメチルアミノアミルアミン、N,N−ジメチルアミノブチルアミン、N,N−ジエチルアミノエチルアミン、N,N−ジエチルアミノプロピルアミン、N,N−ジエチルアミノヘキシルアミン、N,N−ジエチルアミノブチルアミン、N,N−ジエチルアミノペンチルアミン、N,N−ジプロピルアミノブチルアミン、N,N−ジブチルアミノプロピルアミン、N,N−ジブチルアミノエチルアミン、N,N−ジブチルアミノブチルアミン、N,N−ジイソブチルアミノペンチルアミン、N,N−メチルーラウリルアミノプロピルアミン、N,N−エチルーヘキシルアミノエチルアミン、N,N−ジステアリルアミノエチルアミン、N,N−ジオレイルアミノエチルアミン、N,N−ジステアリルアミノブチルアミン、ピペリジン、2−ピペコリン、3−ピペコリン、4−ピペコリン、2,4−ルペチジン、2,6−ルペチジン、3,5−ルペチジン、3−ピペリジンメタノール、ピペコリン酸、イソニペコチン酸、イソニペコチン酸メチル、イソニペコチン酸エチル、2−ピペリジンエタノール、ピロリジン、3−ヒドロキシピロリジン、N−アミノエチルピペリジン、N−アミノエチル−4−ピペコリン、N−アミノエチルモルホリン、N−アミノプロピルピペリジン、N−アミノプロピル−2−ピペコリン、N−アミノプロピル−4−ピペコリン、N−アミノプロピルモルホリン、N−メチルピペラジン、N−ブチルピペラジン、N−メチルホモピペラジン、1−シクロペンチルピペラジン、1−アミノ−4−メチルピペラジン、1−シクロペンチルピペラジン等が挙げられる。 Examples of the amine component used for forming a specific basic group include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl- 1,2- Methylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethyl Aminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N- Tylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecholine, 4-pipecholine, 2,4- Lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N -Methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.
特定の塩基性基を有する誘導体の具体例を以下に示すが、これらに限定されるわけではない。これらの誘導体の中で、アントラキノン系顔料誘導体としては誘導体1〜7、ジケトピロロピロール系顔料誘導体としては誘導体53が挙げられ、本発明では、アントラキノン系顔料誘導体と、ジケトピロロピロール系顔料誘導体とを少なくとも1つずつ必ず含む。さらに、併用する事の出来る誘導体は、単独でまたは2種類以上を混合して用いることができる。 Specific examples of the derivative having a specific basic group are shown below, but are not limited thereto. Among these derivatives, anthraquinone pigment derivatives include derivatives 1 to 7, and diketopyrrolopyrrole pigment derivatives include derivative 53. In the present invention, anthraquinone pigment derivatives and diketopyrrolopyrrole pigment derivatives And at least one each. Furthermore, the derivative | guide_body which can be used together can be used individually or in mixture of 2 or more types.
本発明の赤色着色組成物に含まれる顔料を分散させる顔料担体は、透明樹脂、その前駆体またはそれらの混合物により構成される。透明樹脂は、可視光領域の400〜700nmの全波長領域において透過率が好ましくは80%以上、より好ましくは95%以上の樹脂である。透明樹脂には、熱可塑性樹脂、熱硬化性樹脂、および活性エネルギー線硬化性樹脂が含まれ、その前駆体には、活性エネルギー線照射により硬化して透明樹脂を生成するモノマーもしくはオリゴマーが含まれ、これらを単独で、または2種以上混合して用いることができる。
赤色着色組成物には、該組成物を紫外線照射により硬化するときには、光重合開始剤等が添加される。
The pigment carrier in which the pigment contained in the red coloring composition of the present invention is dispersed is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Transparent resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that are cured by irradiation with active energy rays to form transparent resins. These can be used alone or in admixture of two or more.
When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the red coloring composition.
熱可塑性樹脂としては、例えば、ブチラール樹脂、スチレンーマレイン酸共重合体、塩素化ポリエチレン、塩素化ポリプロピレン、ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重合体、ポリ酢酸ビニル、ポリウレタン系樹脂、ポリエステル樹脂、アクリル系樹脂、アルキッド樹脂、ポリスチレン樹脂、ポリアミド樹脂、ゴム系樹脂、環化ゴム系樹脂、セルロース類、ポリエチレン(HDPE、LDPE)、ポリブタジエン、ポリイミド樹脂等が挙げられる。また、熱硬化性樹脂としては、例えば、エポキシ樹脂、ベンゾグアナミン樹脂、ロジン変性マレイン酸樹脂、ロジン変性フマル酸樹脂、メラミン樹脂、尿素樹脂、フェノール樹脂等が挙げられる。 Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
活性エネルギー線硬化性樹脂としては、水酸基、カルボキシル基、アミノ基等の反応性の置換基を有する線状高分子にイソシアネート基、アルデヒド基、エポキシ基等の反応性置換基を有する(メタ)アクリル化合物やケイヒ酸を反応させて、(メタ)アクリロイル基、スチリル基等の光架橋性基を該線状高分子に導入した樹脂が用いられる。また、スチレン−無水マレイン酸共重合物やα−オレフィン−無水マレイン酸共重合物等の酸無水物を含む線状高分子をヒドロキシアルキル(メタ)アクリレート等の水酸基を有する(メタ)アクリル化合物によりハーフエステル化したものも用いられる。 As the active energy ray-curable resin, a (meth) acryl having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.
顔料担体は、一般式(10)で表される化合物(a)と他のエチレン性不飽和二重結合を有する化合物(b)とを共重合してなる透明樹脂を含有することが好ましい。該透明樹脂は、殆ど全ての顔料に優れた分散効果を発揮するため、着色組成物中において顔料の凝集を防ぎ、顔料が微細に分散した状態を維持する働きをする。そのため、上記透明樹脂を含む顔料担体に顔料を分散してなる本発明の赤色着色組成物を用いてフィルタセグメントを形成した場合には、顔料凝集物の少ないフィルタセグメントを形成することができ、高透過率で明度が高いカラーフィルタを製造することができる。 The pigment carrier preferably contains a transparent resin obtained by copolymerizing the compound (a) represented by the general formula (10) and another compound (b) having an ethylenically unsaturated double bond. Since the transparent resin exhibits an excellent dispersion effect for almost all pigments, it functions to prevent the pigments from agglomerating in the coloring composition and to maintain a finely dispersed state of the pigments. Therefore, when the filter segment is formed using the red coloring composition of the present invention obtained by dispersing the pigment in the pigment carrier containing the transparent resin, a filter segment with few pigment aggregates can be formed. A color filter having high transmittance and brightness can be manufactured.
式(10)
上記透明樹脂の構成成分である一般式(10)で表される化合物(a)は、ベンゼン環のπ電子の効果により顔料表面への吸着/配向性が良好となる。特に(a)がパラクミルフェノールのエチレンオキサイドまたはプロピレンオキサイド変性(メタ)アクリレートである場合には、その立体的な効果も加わり顔料に対しより良好な吸着/配向面を形成できるのでより効果が高い。また、R12のアルキル基の炭素数は1〜20であるが、好ましくは1〜10である。炭素数が1〜10のときはアルキル基が障害となり樹脂同士の接近を抑制し顔料への吸着/配向を促進するが、炭素数が10を越えるとアルキル基の立体障害効果が高くなりベンゼン環の顔料表面への吸着/配向までをも妨げる。これは鎖長が長くなるに従い顕著となり、炭素数が20を越えるとベンゼン環の吸着/配向が極端に低下する。 The compound (a) represented by the general formula (10) which is a constituent component of the transparent resin has good adsorption / orientation on the pigment surface due to the effect of π electrons of the benzene ring. In particular, when (a) is paracumylphenol ethylene oxide or propylene oxide modified (meth) acrylate, its steric effect is added and a better adsorption / orientation plane can be formed on the pigment, which is more effective. . Although the carbon number of the alkyl group of R 12 is from 1 to 20, preferably 1 to 10. When the number of carbon atoms is from 1 to 10, the alkyl group becomes an obstacle to suppress the approach between the resins and promote the adsorption / orientation to the pigment. Even the adsorption / orientation to the pigment surface is hindered. This becomes more prominent as the chain length becomes longer, and when the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely lowered.
化合物(a)としては、フェノールエチレンオキサイド変性(メタ)アクリレート、パラクミルフェノールエチレンオキサイド変性(メタ)アクリレート、ノニルフェノールエチレンオキサイド変性(メタ)アクリレート、ノニルフェノールプロピレンオキサイド変性(メタ)アクリレート等が挙げられる。 Examples of the compound (a) include phenol ethylene oxide modified (meth) acrylate, paracumylphenol ethylene oxide modified (meth) acrylate, nonylphenol ethylene oxide modified (meth) acrylate, nonylphenol propylene oxide modified (meth) acrylate and the like.
化合物(b)としては、(メタ)アクリル酸、メチル(メタ)アクリレート、エチル(メタ)アクリレート、(イソ)プロピル(メタ)アクリレート、(イソ)ブチル(メタ)アクリレート、(イソ)ペンチル(メタ)アクリレート、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、ベンジル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、グリシジル(メタ)アクリレート、イソボニル(メタ)アクリレートアシッドホスホオキシエチル(メタ)アクリレート、アシッドホスホオキシプロピル(メタ)アクリレート、3クロロ2アシッドホスホオキシエチル(メタ)アクリレート、アシッドホスホオキシポリエチレングリコールモノ(メタ)アクリレート、等が挙げられる。 As the compound (b), (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate, (iso) pentyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) acrylate acid phosphooxyethyl (meth) Examples thereof include acrylate, acid phosphooxypropyl (meth) acrylate, 3 chloro 2-acid phosphooxyethyl (meth) acrylate, and acid phosphooxypolyethylene glycol mono (meth) acrylate.
上記透明樹脂を構成する化合物中の化合物(a)の割合は、好ましくは0.1〜50重量%、より好ましくは10〜35重量%である。化合物(a)の割合が0.1重量%より少ないと充分な顔料の分散効果を得ることができず、50重量%より多いと着色組成物中の他の構成成分との相溶性が低下し、モノマーや光重合開始剤の析出が起こることがある。
上記透明樹脂の重量平均分子量(Mw)は、好ましくは5000〜100000であり、さらに好ましくは10000〜50000である。
The proportion of the compound (a) in the compound constituting the transparent resin is preferably 0.1 to 50% by weight, more preferably 10 to 35% by weight. When the proportion of the compound (a) is less than 0.1% by weight, a sufficient pigment dispersion effect cannot be obtained, and when it is more than 50% by weight, the compatibility with other components in the coloring composition is lowered. In some cases, precipitation of the monomer or photopolymerization initiator may occur.
The weight average molecular weight (Mw) of the transparent resin is preferably 5,000 to 100,000, more preferably 10,000 to 50,000.
モノマー、オリゴマーとしては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、β−カルボキシエチル(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、1, 6−ヘキサンジオールジグリシジルエーテルジ(メタ)アクリレート、ビスフェノールAジグリシジルエーテルジ(メタ)アクリレート、ネオペンチルグリコールジグリシジルエーテルジ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリシクロデカニル(メタ)アクリレート、エステルアクリレート、メチロール化メラミンの(メタ)アクリル酸エステル、エポキシ(メタ)アクリレート、ウレタンアクリレート等の各種アクリル酸エステルおよびメタクリル酸エステル、(メタ)アクリル酸、スチレン、酢酸ビニル、ヒドロキシエチルビニルエーテル、エチレングリコールジビニルエーテル、ペンタエリスリトールトリビニルエーテル、(メタ)アクリルアミド、N−ヒドロキシメチル(メタ)アクリルアミド、N−ビニルホルムアミド、アクリロニトリル等が挙げられ、これらを単独でまたは2種類以上混合して用いることができる。 As monomers and oligomers, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopen Tylglycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane Various acrylates and methacrylates such as acrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide , N-vinylformamide, acrylonitrile and the like, and these can be used alone or in admixture of two or more.
光重合開始剤としては、4−フェノキシジクロロアセトフェノン、4−t−ブチル−ジクロロアセトフェノン、ジエトキシアセトフェノン、1−(4−イソプロピルフェニル)−2−ヒドロキシ−2−メチルプロパン−1−オン、1−ヒドロキシシクロヘキシルフェニルケトン、2−ベンジル−2−ジメチルアミノ−1−(4−モルフォリノフェニル)−ブタン−1−オン、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルフォリノプロパン−1−オン等のアセトフェノン系光重合開始剤、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンジルジメチルケタール等のベンゾイン系光重合開始剤、ベンゾフェノン、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、4−フェニルベンゾフェノン、ヒドロキシベンゾフェノン、アクリル化ベンゾフェノン、4−ベンゾイル−4'−メチルジフェニルサルファイド等のベンゾフェノン系光重合開始剤、チオキサンソン、2−クロルチオキサンソン、2−メチルチオキサンソン、イソプロピルチオキサンソン、2,4−ジイソプロピルチオキサンソン等のチオキサンソン系光重合開始剤、2,4,6−トリクロロ−s−トリアジン、2−フェニル−4,6−ビス(トリクロロメチル)−s−トリアジン、2−(p−メトキシフェニル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2−(p−トリル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2−ピペロニル−4,6−ビス(トリクロロメチル)−s−トリアジン、2,4−ビス(トリクロロメチル)−6−スチリル−s−トリアジン、2−(ナフト−1−イル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2−(4−メトキシ−ナフト−1−イル)−4,6−ビス(トリクロロメチル)−s−トリアジン、2,4−トリクロロメチル−(ピペロニル)−6−トリアジン、2,4−トリクロロメチル(4'−メトキシスチリル)−6−トリアジン等のトリアジン系光重合開始剤、ボレート系光重合開始剤、カルバゾール系光重合開始剤、イミダゾール系光重合開始剤等が用いられる。 Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenone photopolymerization initiators such as -1-one, benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4 Benzophenone photopolymerization initiators such as phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2 Thioxanthone photopolymerization initiators such as 2,4-diisopropylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p -Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (Trichloromethyl) -s-triazine, 2,4-bis (trick (Romethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, etc. A polymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, an imidazole photopolymerization initiator, or the like is used.
上記光重合開始剤は、単独あるいは2種以上混合して用いるが、増感剤として、α−アシロキシエステル、アシルフォスフィンオキサイド、メチルフェニルグリオキシレート、ベンジル、9,10−フェナンスレンキノン、カンファーキノン、エチルアンスラキノン、4,4'−ジエチルイソフタロフェノン、3,3',4,4'−テトラ(t−ブチルパーオキシカルボニル)ベンゾフェノン、4,4'−ジエチルアミノベンゾフェノン等の化合物を併用することもできる。 The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.
本発明の赤色着色組成物は、溶剤現像型あるいはアルカリ現像型着色レジストの形態で調整することができる。着色レジストは、熱可塑性樹脂、熱硬化性樹脂または活性エネルギー線硬化性樹脂とモノマーを含む顔料担体中に顔料を分散させたものであり、数種類以上の顔料からなる顔料組成物を、必要に応じて光重合開始剤と共に、顔料担体中に、三本ロールミル、二本ロールミル、サンドミル、ニーダー、アトライター等の各種分散手段を用いて微細に分散して製造することができる。また、本発明の赤色着色組成物は、数種類以上の顔料を別々に顔料担体に分散したものを混合して製造することもできる。 The red coloring composition of the present invention can be adjusted in the form of a solvent developing type or alkali developing type colored resist. The colored resist is obtained by dispersing a pigment in a pigment carrier containing a thermoplastic resin, a thermosetting resin or an active energy ray curable resin and a monomer, and a pigment composition composed of several or more types of pigments, if necessary. In addition to the photopolymerization initiator, it can be produced by finely dispersing in a pigment carrier using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. The red coloring composition of the present invention can also be produced by mixing several pigments separately dispersed on a pigment carrier.
顔料を顔料担体中に分散する際には、適宜、樹脂型顔料分散剤、界面活性剤等の分散助剤を用いることができる。分散助剤は、顔料の分散に優れ、分散後の顔料の再凝集を防止する効果が大きいので、分散助剤を用いて顔料を顔料担体中に分散してなる着色組成物を用いた場合には、透明性に優れたカラーフィルタが得られる。 When dispersing the pigment in the pigment carrier, a dispersion aid such as a resin-type pigment dispersant and a surfactant can be appropriately used. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in the pigment carrier using the dispersion aid is used. Provides a color filter excellent in transparency.
樹脂型顔料分散剤は、顔料に吸着する性質を有する顔料親和性部位と、顔料担体と相溶性のある部位とを有し、顔料に吸着して顔料の顔料担体への分散を安定化する働きをするものである。樹脂型顔料分散剤として具体的には、ポリウレタン、ポリアクリレートなどのポリカルボン酸エステル、不飽和ポリアミド、ポリカルボン酸、ポリカルボン酸(部分)アミン塩、ポリカルボン酸アンモニウム塩、ポリカルボン酸アルキルアミン塩、ポリシロキサン、長鎖ポリアミノアマイドリン酸塩、水酸基含有ポリカルボン酸エステルや、これらの変性物、ポリ(低級アルキレンイミン)と遊離のカルボキシル基を有するポリエステルとの反応により形成されたアミドやその塩などの油性分散剤、(メタ)アクリル酸−スチレン共重合体、(メタ)アクリル酸−(メタ)アクリル酸エステル共重合体、スチレン−マレイン酸共重合体、ポリビニルアルコール、ポリビニルピロリドンなどの水溶性樹脂や水溶性高分子化合物、ポリエステル系、変性ポリアクリレート系、エチレンオキサイド/プロピレンオキサイド付加化合物、燐酸エステル系等が用いられ、これらは単独でまたは2種以上を混合して用いることができる。 The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and acts to stabilize the dispersion of the pigment on the pigment carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.
界面活性剤としては、ラウリル硫酸ソーダ、ポリオキシエチレンアルキルエーテル硫酸塩、ドデシルベンゼンスルホン酸ソーダ、スチレン−アクリル酸共重合体のアルカリ塩、ステアリン酸ナトリウム、アルキルナフタリンスルホン酸ナトリウム、アルキルジフェニルエーテルジスルホン酸ナトリウム、ラウリル硫酸モノエタノールアミン、ラウリル硫酸トリエタノールアミン、ラウリル硫酸アンモニウム、ステアリン酸モノエタノールアミン、ステアリン酸ナトリウム、ラウリル硫酸ナトリウム、スチレン−アクリル酸共重合体のモノエタノールアミン、ポリオキシエチレンアルキルエーテルリン酸エステルなどのアニオン性界面活性剤;ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンアルキルエーテルリン酸エステル、ポリオキシエチレンソルビタンモノステアレート、ポリエチレングリコールモノラウレートなどのノニオン性界面活性剤;アルキル4級アンモニウム塩やそれらのエチレンオキサイド付加物などのカオチン性界面活性剤;アルキルジメチルアミノ酢酸ベタインなどのアルキルベタイン、アルキルイミダゾリンなどの両性界面活性剤が挙げられ、これらは単独でまたは2種以上を混合して用いることができる。 Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. , Lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Anionic surfactants such as: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as nylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactants: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more.
本発明の赤色着色組成物には、顔料を充分に顔料担体中に分散させ、ガラス基板等の透明基板上に乾燥膜厚が0.5〜3μmとなるように塗布してフィルタセグメントを形成することを容易にするために溶剤を含有させることができる。溶剤としては、例えばシクロヘキサノン、エチルセロソルブアセテート、ブチルセロソルブアセテート、1−メトキシ−2−プロピルアセテート、ジエチレングリコールジメチルエーテル、エチルベンゼン、エチレングリコールジエチルエーテル、キシレン、エチルセロソルブ、メチル−nアミルケトン、プロピレングリコールモノメチルエーテルトルエン、メチルエチルケトン、酢酸エチル、メタノール、エタノール、イソプロピルアルコール、ブタノール、イソブチルケトン、石油系溶剤等が挙げられ、これらを単独でもしくは混合して用いる。 In the red coloring composition of the present invention, a pigment is sufficiently dispersed in a pigment carrier, and applied to a transparent substrate such as a glass substrate so as to have a dry film thickness of 0.5 to 3 μm to form a filter segment. In order to facilitate this, a solvent can be included. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.
また、本発明の赤色着色組成物には、組成物の経時粘度を安定化させるために貯蔵安定剤を含有させることができる。貯蔵安定剤としては、例えばベンジルトリメチルクロライド、ジエチルヒドロキシアミンなどの4級アンモニウムクロライド、乳酸、シュウ酸などの有機酸およびそのメチルエーテル、t−ブチルピロカテコール、トリエチルホスフィン、トリフェニルフォスフィンなどの有機ホスフィン、亜リン酸塩等が挙げられる。
顔料は、赤色着色組成物中に合計して1.5〜12重量%の割合で含有されることが好ましい。また、顔料は、最終フィルタセグメント中に合計して好ましくは10〜40重量%、より好ましくは20〜40重量%の割合で含有され、その残部は、顔料担体により提供される樹脂質バインダーから実質的になる。
In addition, the red coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite.
The pigment is preferably contained in the red coloring composition in a proportion of 1.5 to 12% by weight in total. In addition, the pigment is preferably contained in the final filter segment in a proportion of preferably 10 to 40% by weight, more preferably 20 to 40% by weight, with the remainder being substantially from the resinous binder provided by the pigment carrier. Become.
本発明の赤色着色組成物は、遠心分離、焼結フィルタ、メンブレンフィルタ等の手段にて、5μm以上の粗大粒子、好ましくは1μm以上の粗大粒子、さらに好ましくは0.5μm以上の粗大粒子および混入した塵の除去を行うことが好ましい。 The red coloring composition of the present invention is prepared by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles It is preferable to remove the dust.
次に、カラーフィルタについて説明する。
本発明のカラーフィルタは、透明あるいは反射基板上に、R(赤)、G(緑)、B(青)の3色のフィルタセグメントが形成されたものである。赤色のフィルタセグメントは、印刷法またはフォトリソグラフィー法により、本発明の着色組成物を用いて形成される。
緑色フィルタセグメントは、通常の緑色着色組成物を用いて形成することができる。緑色着色組成物は、赤色顔料の代わりに、例えば、C.I.Pigment Green 7、10、36、37等の緑色顔料を用いて得られる組成物である。緑色着色組成物には、上記の黄色顔料を併用することができる。
Next, the color filter will be described.
In the color filter of the present invention, three color filter segments of R (red), G (green), and B (blue) are formed on a transparent or reflective substrate. The red filter segment is formed by using the coloring composition of the present invention by a printing method or a photolithography method.
The green filter segment can be formed using a normal green coloring composition. The green coloring composition can be replaced with, for example, C.I. I. This is a composition obtained using a green pigment such as Pigment Green 7, 10, 36, 37. The yellow pigment can be used in combination with the green coloring composition.
青色フィルタセグメントは、通常の青色着色組成物を用いて形成することができる。青色着色組成物は、赤色顔料の代わりに、例えばC.I.Pigment Blue 15、15:1、15:2、15:3、15:4、15:6、16、22、60、64等の青色顔料を用いて得られる組成物である。青色着色組成物には、C.I.Pigment Violet 1、19、23、27、29、30、32、37、40、42、50等の紫色顔料を併用することができる。 The blue filter segment can be formed using a normal blue coloring composition. Instead of the red pigment, the blue coloring composition is, for example, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.
透明基板としては、石英ガラス、ホウケイ酸ガラス、アルミナケイ酸塩ガラス、表面をシリカコートしたソーダライムガラスなどのガラス板や、ポリカーボネート、ポリメタクリル酸メチル、ポリエチレンテレフタレートなどの樹脂板が用いられる。
反射基板としては、シリコンや、前記の透明基板上にアルミニウム、銀、銀/銅/パラジウム合金薄膜などを形成したものが用いられる。
As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is coated with silica, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
As the reflective substrate, silicon or a substrate in which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed on the transparent substrate is used.
印刷法による各色フィルタセグメントの形成は、上記各種の印刷インキとして調製した着色組成物の印刷と乾燥を繰り返すだけでパターン化ができるため、カラーフィルタの製造法としては、低コストで量産性に優れている。さらに、印刷技術の発展により高い寸法精度および平滑度を有する微細パターンの印刷を行うことができる。印刷を行うためには、印刷の版上にて、あるいはブランケット上にてインキが乾燥、固化しないような組成とすることが好ましい。また、印刷機上でのインキの流動性の制御も重要であり、分散剤や体質顔料によるインキ粘度の調整を行うこともできる。 The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.
フォトリソグラフィー法により各色フィルタセグメントを形成する場合は、上記溶剤現像型あるいはアルカリ現像型着色レジスト材として調製した着色組成物を、透明基板上に、スプレーコートやスピンコート、スリットコート、ロールコート等の塗布方法により、乾燥膜厚が0.5〜3μmとなるように塗布する。必要により乾燥された膜には、この膜と接触あるいは非接触状態で設けられた所定のパターンを有するマスクを通して紫外線露光を行う。その後、溶剤またはアルカリ現像液に浸漬するか、もしくはスプレーなどにより現像液を噴霧して未硬化部を除去し所望のパターンを形成したのち、同様の操作を他色について繰り返してカラーフィルタを製造することができる。さらに、着色レジスト材の重合を促進するため、必要に応じて加熱を施すこともできる。フォトリソグラフィー法によれば、上記印刷法より精度の高いカラーフィルタが製造できる。 When forming each color filter segment by a photolithography method, the colored composition prepared as the solvent developing type or alkali developing type colored resist material is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. It is applied by a coating method so that the dry film thickness is 0.5 to 3 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.
現像に際しては、アルカリ現像液として炭酸ナトリウム、水酸化ナトリウム等の水溶液が使用され、ジメチルベンジルアミン、トリエタノールアミン等の有機アルカリを用いることもできる。また、現像液には、消泡剤や界面活性剤を添加することもできる。
なお、紫外線露光感度を上げるために、上記着色レジスト材を塗布乾燥後、水溶性あるいはアルカリ可溶性樹脂、例えばポリビニルアルコールや水溶性アクリル樹脂等を塗布乾燥し酸素による重合阻害を防止する膜を形成した後、紫外線露光を行うこともできる。
In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.
本発明のカラーフィルタは、上記方法の他に電着法、転写法などにより製造することができるが、本発明の着色組成物は、いずれの方法にも用いることができる。なお、電着法は、透明基板上に形成した透明導電膜を利用して、コロイド粒子の電気泳動により各色フィルタセグメントを透明導電膜の上に電着形成することでカラーフィルタを製造する方法である。
また、転写法は剥離性の転写ベースシートの表面に、あらかじめカラーフィルタ層を形成しておき、このカラーフィルタ層を所望の透明基板に転写させる方法である。
The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there.
The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.
透明基板あるいは反射基板上にフィルタセグメントを形成する前に、あらかじめブラックマトリクスを形成しておくと、液晶表示パネルのコントラスト比を一層高めることができる。ブラックマトリクスとしては、クロムやクロム/酸化クロムの多層膜、窒化チタニウムなどの無機膜や、遮光剤を分散した樹脂膜が用いられるが、これらに限定されない。また、前記の透明基板あるいは反射基板上に薄膜トランジスター(TFT)をあらかじめ形成しておき、その後にフィルタセグメントを形成することもできる。TFT基板上にフィルタセグメントを形成することにより、液晶表示パネルの開口率を高め、輝度を向上させることができる。 If a black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast ratio of the liquid crystal display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.
本発明のカラーフィルタ上には、必要に応じてオーバーコート膜や柱状スペーサー、透明導電膜、液晶配向膜などが形成される。
カラーフィルタは、シール剤を用いて対向基板と張り合わせ、シール部に設けられた注入口から液晶を注入したのち注入口を封止し、必要に応じて偏光膜や位相差膜を基板の外側に張り合わせることにより、液晶表示パネルが製造される。
かかる液晶表示パネルは、ツイステッド・ネマティック(TN)、スーパー・ツイステッド・ネマティック(STN)、イン・プレーン・スイッチング(IPS)、ヴァーティカリー・アライメント(VA)、オプティカリー・コンベンセンド・ベンド(OCB)などのカラーフィルタを使用してカラー化を行う液晶表示モードに使用することができる。
On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.
The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.
Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.
以下に,実施例により本発明を説明する。なお、実施例中の「部」および「%」とは、「重量部」および「重量%」をそれぞれ表す。
(アクリル樹脂溶液1の調製)
セパラブル4口フラスコに温度計、冷却管、窒素ガス導入管、撹拌装置を取り付けた反応容器にシクロヘキサノン800部を入れ、容器に窒素ガスを注入しながら100℃に加熱して、同温度で滴下管よりスチレン60.0部、メタクリル酸60.0部、メチルメタクリレート65.0部、ブチルメタクリレート65.0部、アゾビスイソブチロニトリル10.0部の混合物を1時間かけて滴下して重合反応を行った。
滴下後さらに100℃で3時間反応させた後、アゾビスイソブチロニトリル2.0部をシクロヘキサノン50部で溶解させたものを添加し、さらに100℃で1時間反応を続けて、重量平均分子量が約40000(GPCによる測定)のアクリル樹脂の溶液を得た。
室温まで冷却した後、樹脂溶液約2gをサンプリングして180℃、20分加熱乾燥して不揮発分を測定し、先に合成した樹脂溶液に不揮発分が20%になるようにシクロヘキサノンを添加してアクリル樹脂溶液1を調製した。
Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
(Preparation of acrylic resin solution 1)
Place 800 parts of cyclohexanone in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 100 ° C. while injecting nitrogen gas into the vessel. A mixture of 60.0 parts of styrene, 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate, and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to polymerize the reaction. Went.
After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain a weight average molecular weight. Of about 40000 (measured by GPC).
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. Acrylic resin solution 1 was prepared.
(アクリル樹脂溶液2の調製)
アクリル樹脂溶液1の調製と同様の反応容器にシクロヘキサノン70.0部を仕込み、80℃に昇温し、反応容器内を窒素置換した後、滴下管よりn−ブチルメタクリレート13.3部、2−ヒドロキシエチルメタクリレート4.6部、メタクリル酸4.3部、パラクミルフェノールエチレンオキサイド変性アクリレート(東亜合成株式会社製「アロニックスM110」)7.4部、2,2'−アゾビスイソブチロニトリル0.4部の混合物を2時間かけて滴下した。滴下終了後、更に3時間反応を継続し、固形分30%、重量平均分子量26000のアクリル樹脂の溶液を得た。
室温まで冷却した後、樹脂溶液約2gをサンプリングして180℃、20分加熱乾燥して不揮発分を測定し、先に合成した樹脂溶液に不揮発分が20%になるようにシクロヘキサノンを添加してアクリル樹脂溶液2を調製した。
(Preparation of acrylic resin solution 2)
In a reaction vessel similar to the preparation of the acrylic resin solution 1, 70.0 parts of cyclohexanone was charged, the temperature was raised to 80 ° C., and the inside of the reaction vessel was purged with nitrogen, then 13.3 parts of n-butyl methacrylate, 4.6 parts of hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.), 2,2′-azobisisobutyronitrile 0 4 parts of the mixture were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% and a weight average molecular weight of 26000.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. Acrylic resin solution 2 was prepared.
[実施例1〜6、比較例1、2]
(赤色処理顔料1の調製)
アントラキノン系赤色顔料C.I.Pigment Red 177(チバスペシャルティケミカルズ社製「クロモフタルレッド A2B」):500部、塩化ナトリウム:500部、およびジエチレングリコール:250部をステンレス製1ガロンニーダー(井上製作所製)に仕込み、120℃で8時間混練した。次に、この混練物を5リットルの温水に投入し、70℃に加熱しながら1時間攪拌してスラリー状とし、濾過、水洗を繰り返して塩化ナトリウム及びジエチレングリコールを除いた後、80℃で一昼夜乾燥し、赤色処理顔料1を得た。
[Examples 1 to 6, Comparative Examples 1 and 2]
(Preparation of red treated pigment 1)
Anthraquinone red pigment C.I. I. Pigment Red 177 (“Chromophthalred A2B” manufactured by Ciba Specialty Chemicals): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) at 120 ° C. for 8 hours. Kneaded. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, red-treated pigment 1 was obtained.
(赤色処理顔料2の調製)
ジケトピロロピロール系赤色顔料C.I.Pigment Red 254(チバスペシャルティケミカルズ社製「イルガジンジケトピロロピロール RED BO」):500部、塩化ナトリウム:500部、およびジエチレングリコール:250部をステンレス製1ガロンニーダー(井上製作所製)に仕込み、120℃で8時間混練した。次に、この混練物を5リットルの温水に投入し、70℃に加熱しながら1時間攪拌してスラリー状とし、濾過、水洗を繰り返して塩化ナトリウム及びジエチレングリコールを除いた後、80℃で一昼夜乾燥し、赤色処理顔料2を得た。
(Preparation of red treated pigment 2)
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 (“Irgazine diketopyrrolopyrrole RED BO” manufactured by Ciba Specialty Chemicals): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) at 120 ° C. For 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, red-treated pigment 2 was obtained.
(顔料分散体の製造方法)
表1に示す組成の顔料および誘導体の混合物15.0部、アクリル樹脂溶液1を50.0部(実施例2、3ではアクリル樹脂溶液2を用いた)、シクロヘキサノン60.0部を均一に撹拌混合した後、直径1mmのジルコニアビーズを用いて、アイガーミル(アイガージャパン社製「ミニモデルM−250 MKII」)で3時間分散した後、5μmのフィルタで濾過し、顔料分散体を作製した。
ただし、実施例4は参考例である。
(Method for producing pigment dispersion)
15.0 parts of a mixture of pigments and derivatives having the composition shown in Table 1, 50.0 parts of the acrylic resin solution 1 (the acrylic resin solution 2 was used in Examples 2 and 3), and 60.0 parts of cyclohexanone were uniformly stirred. After mixing, using a zirconia bead having a diameter of 1 mm, the mixture was dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then filtered with a 5 μm filter to prepare a pigment dispersion.
However, Example 4 is a reference example.
*1 PY139:C.I.Pigment Yellow 139
(チバスペシャルティケミカルズ社製「イルガフォアイエロー 2R−CF」)
PO71:C.I.Pigment Orange 71
(チバスペシャルティケミカルズ社製「クロモフタール ジケトピロロピロール オレンジTR」)
*2 色素誘導体は、[発明を実施するための形態]中に示す誘導体を意味する。
* 1 PY139: C.I. I. Pigment Yellow 139
("Irgafore Yellow 2R-CF" manufactured by Ciba Specialty Chemicals)
PO71: C.I. I. Pigment Orange 71
("Chromophthal Diketopyrrolopyrrole Orange TR" manufactured by Ciba Specialty Chemicals)
* 2 A pigment derivative means a derivative shown in [Mode for Carrying Out the Invention].
(レジスト材の製造方法)
ついで、下記組成の混合物を均一になるように攪拌混合した後、1μmのフィルタで濾過して、アルカリ現像型赤色レジスト材を得た。
表1に示す混合物の顔料分散体 60.0部
光重合開始剤 1.2部
(チバスペシャルティケミカルズ社製「イルガキュア907」)
トリメチロールプロパントリアクリレート 4.2部
(新中村化学株式会社製「NKエステルATMPT」)
増感剤(保土ヶ谷化学株式会社製「EAB−F」) 1.4部
アクリル樹脂溶液1 11.0部
シクロヘキサノン 23.2部
(Method for producing resist material)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain an alkali developing red resist material.
Pigment dispersion of mixture shown in Table 1 60.0 parts Photopolymerization initiator 1.2 parts ("Irgacure 907" manufactured by Ciba Specialty Chemicals)
4.2 parts of trimethylolpropane triacrylate (“NK ESTER ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 1.4 parts acrylic resin solution 1 11.0 parts cyclohexanone 23.2 parts
(塗膜の作製)
得られたレジスト材の20rpm、25℃における粘度をE型粘度計(ELD型粘度計:東機産業社製)で測定し、評価した。また、得られたレジスト材を板厚0.7mmの360mm×465mmサイズの基板に平均膜厚が1.8μmになるようにスピンコートし、70℃で30分乾燥した後、中心部の膜厚(Aとする)と対角線上で中心から200mm部分の膜厚4点の平均値(Bとする)を測定し、下式により膜厚の均一性を評価した。評価結果を表2に示す。
(A−B)×100/{(A+B)/2} [%]
また、得られたレジスト材を、100mm×100mm、1.3mm厚のガラス基板上に、スピンコーターを用いて、x=0.640、y=0.330近傍になるような膜厚に塗布した。次に、70℃で20分乾燥後、超高圧水銀ランプを用いて、積算光量150mJで紫外線露光を行った。塗布基板を230℃で1時間加熱して放冷後、顕微分光光度計(オリンパス光学株式会社製「OSP−SP100」)を用いて、得られた赤色塗膜のC光源での明度(Y)を求めた。また、硬化塗膜の膜厚を触針式表面形状測定器(Veeco社製「Dektak8」)で測定した。評価結果を表2に示す。
(Preparation of coating film)
The viscosity of the obtained resist material at 20 rpm and 25 ° C. was measured with an E-type viscometer (ELD viscometer: manufactured by Toki Sangyo Co., Ltd.) and evaluated. In addition, the obtained resist material was spin-coated on a 360 mm × 465 mm size substrate having a thickness of 0.7 mm so that the average film thickness was 1.8 μm, dried at 70 ° C. for 30 minutes, and then the film thickness in the center portion. The average value of four film thicknesses (referred to as B) in a 200 mm portion from the center on the diagonal line (measured as A) was measured, and the film thickness uniformity was evaluated by the following formula. The evaluation results are shown in Table 2.
(A−B) × 100 / {(A + B) / 2} [%]
Further, the obtained resist material was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.3 mm using a spin coater so that x = 0.640 and y = 0.330 were obtained. . Next, after drying at 70 ° C. for 20 minutes, ultraviolet exposure was performed with an integrated light amount of 150 mJ using an ultrahigh pressure mercury lamp. The coated substrate was heated at 230 ° C. for 1 hour and allowed to cool, and then the brightness (Y) of the obtained red coating film with a C light source using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) Asked. Moreover, the film thickness of the cured coating film was measured with a stylus type surface shape measuring instrument (“Dektak 8” manufactured by Veeco). The evaluation results are shown in Table 2.
表2に示すように、比較例1と比べると、実施例1〜6では、2種類それぞれの赤色顔料に組み合わせる誘導体種の適正化を図ることにより、低粘度で安定なレジスト材が得られ、均一な塗布硬化膜を得ることができている。 As shown in Table 2, compared with Comparative Example 1, in Examples 1 to 6, a low-viscosity and stable resist material can be obtained by optimizing the derivative species combined with each of the two types of red pigments. A uniform coating cured film can be obtained.
Claims (7)
式(1)
式(4)
式(8)
Formula (1)
Formula (4)
Formula (8)
式(10)
Formula (10)
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JP2002194244A (en) * | 2000-12-25 | 2002-07-10 | Fuji Photo Film Co Ltd | Pigment dispersion composition, coloring photosensitive composition obtained by using the same and color filter |
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JP4461681B2 (en) * | 2002-01-29 | 2010-05-12 | 東洋インキ製造株式会社 | Coloring composition for color filter and color filter |
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