JP2019008014A - Photosensitive colored composition for color filter and color filter - Google Patents

Abstract

To provide a photosensitive colored composition from which a green pixel can be formed that has good weather resistance and maintains a high brightness, and to provide a color filter including a green pixel formed from the above photosensitive colored composition, and a color liquid crystal display element including the color filter.SOLUTION: A photosensitive colored composition for a color filter is provided, which comprises a halogenated metal phthalocyanine (A), a quinophthalone-based yellow pigment (B), and a photoacid generator (C), in which the halogenated metal phthalocyanine (A) is at least one compound selected from halogenated copper phthalocyanine, halogenated zinc phthalocyanine and halogenated aluminum phthalocyanine, and the photoacid generator (C) comprises a triarylsulfonium compound (C1).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive coloring composition 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 including a filter segment formed using the same. .

  As a method of forming a color filter using a photosensitive coloring composition, a coating film of the photosensitive coloring composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern is formed in advance, and a predetermined pattern is formed. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask, developing and dissolving and removing unexposed portions, and then post-baking (for example, Patent Document 1) , See Patent Document 2).

  A liquid crystal display device having such a color filter is required to have high brightness and an expanded color reproduction area, and for this reason, color filters are required to have higher light transmittance and higher color purity in recent years. ing. For green pixels, a combination of a pigment composition containing a metal halide phthalocyanine pigment and a quinophthalone yellow pigment composition is known as a material that can provide a color filter with high brightness and a wide color reproduction range. (For example, refer to Patent Document 3). However, a green pixel formed using a combination of a pigment composition containing a halogenated metal phthalocyanine pigment and a quinophthalone-based yellow pigment composition is an LED backlight in an oxygen-blocking environment such as that incorporated in a liquid crystal panel. In this case, there is a problem that the brightness of the green pixel decreases with time under conditions of constant temperature and humidity (65 ° C./95%). (Hereinafter referred to as weather resistance.)

JP-A-2-144502 JP-A-3-53201 JP 2007-284589 A JP 2010-250225 A JP 2009-35671 A

  The objective of this invention is providing the photosensitive coloring composition which can form the green pixel which has favorable weather resistance and maintains high brightness with respect to the said subject. Furthermore, it is providing the color filter provided with the green pixel formed from the said photosensitive coloring composition, and the color liquid crystal display element which comprises the said color filter.

In order to solve the above problems, the present inventors have conducted intensive research,
It has been found that a photosensitive coloring composition containing a halogenated metal phthalocyanine (A), a quinophthalone yellow pigment (B) and a photoacid generator (C) is excellent in weather resistance.

  That is, the present invention is a photosensitive coloring composition containing a metal halide phthalocyanine (A), a quinophthalone yellow pigment (B) and a photoacid generator (C), wherein the metal halide phthalocyanine (A) The present invention relates to a photosensitive coloring composition for a color filter, which is at least one selected from copper halide phthalocyanine, zinc halide phthalocyanine, and halogenated aluminum phthalocyanine.

  The present invention also relates to the above photosensitive coloring composition for color filters, wherein the content of the photoacid generator (C) is 1 to 4% by weight in the total solid content of the photosensitive coloring composition. .

［一般式（１）中、Ｒ^１〜Ｒ^１３は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有しても良いアルキル基、置換基を有しても良いアルコキシル基、置換基を有しても良いアリール基、−ＳＯ_３Ｈ；−ＣＯＯＨ；およびこれら酸性基の１価〜３価の金属塩；アルキルアンモニウム塩、置換基を有しても良いフタルイミドメチル基、または置換基を有しても良いスルファモイル基を示す。
ただし、Ｒ^１〜Ｒ^４、および／または、Ｒ^１０〜Ｒ^１３の隣接した基は、一体となって、置換基を有してもよい芳香環を形成する。 The present invention also relates to the above photosensitive coloring composition for color filters, wherein the quinophthalone yellow pigment (B) is a quinophthalone yellow pigment represented by the following general formula (1).
General formula (1)

[In General Formula (1), R ^{1 to} R ¹³ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. An aryl group which may have, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, phthalimidomethyl groups which may have a substituent, or substituents; The sulfamoyl group which may have is shown.
However, the adjacent groups of R ^{1 to} R ⁴ and / or R ^{10 to} R ¹³ together form an aromatic ring that may have a substituent.

  The present invention also relates to the above color composition for a color filter, which further contains a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also relates to a color filter comprising a filter segment formed from the green photosensitive coloring composition on a substrate.

  By using the photosensitive coloring composition of the present invention, a green pixel having good weather resistance and high brightness can be formed. Therefore, a color filter including a green pixel formed using the photosensitive coloring composition of the present invention includes, for example, a transmissive or reflective color liquid crystal display element, a color imaging tube element, a color sensor, and an organic EL display. It is extremely useful for devices, electronic paper, and the like.

Schematic which shows a weather resistance test method.

  The photosensitive coloring composition of the present invention comprises, as a halogenated metal phthalocyanine (A), at least one selected from a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine and a halogenated aluminum phthalocyanine, a photoacid generator (C), And a quinophthalone pigment (B).

<Halogenated metal phthalocyanine (A)>
Representative examples of the metal halide phthalocyanine pigment (A) include halogenated copper phthalocyanine, halogenated zinc phthalocyanine, and halogenated aluminum phthalocyanine.

  A typical copper halide phthalocyanine pigment represented by a color index (CI) number is C.I. I. Pigment green 36, C.I. I. And CI Pigment Green 7.

  A typical zinc halide phthalocyanine pigment represented by a color index (CI) number is C.I. I. And CI Pigment Green 58. By using a halogenated zinc phthalocyanine pigment, it is possible to obtain a high brightness not obtained with other green pigments. Furthermore, what was obtained by the well-known manufacturing method can be used. In particular, the amount of acidic functional groups on the pigment surface is preferably 100 μmol when measured using n-hexylamine as a basic substance by the method described in Coloring Materials, 67 [9], 547-554 (1994). / G or more, more preferably 200 μmol / g or more.

  Other green pigments that can be used in combination with a halogenated zinc phthalocyanine pigment as the halogenated metal phthalocyanine (A) include C.I. I. And aluminum phthalocyanine pigments described in CI Pigment Green 7, 10, 36, 37, Japanese Patent No. 4893859, and the like. Of these, C.I. I. Pigment Green 7C. I. Pigment Green 36, or an aluminum phthalocyanine pigment described in Japanese Patent No. 4893859.

  The photosensitive coloring composition of the present invention includes not only a halogenated copper phthalocyanine pigment, a halogenated zinc phthalocyanine pigment, and a halogenated gold aluminum phthalocyanine as a halogenated metal phthalocyanine (A), but also for the purpose of color adjustment and complementary color. Green pigments and yellow pigments can also be used in combination. One or two or more pigments to be used in combination can be appropriately selected.

<Kinophthalone yellow pigment (B)>
Examples of the quinophthalone yellow pigment include C.I. I. Pigment yellow 138, 231 and the like.

［一般式（１）中、Ｒ^１〜Ｒ^１３は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有しても良いアルキル基、置換基を有しても良いアルコキシル基、置換基を有しても良いアリール基、−ＳＯ_３Ｈ；−ＣＯＯＨ；およびこれら酸性基の１価〜３価の金属塩；アルキルアンモニウム塩、置換基を有しても良いフタルイミドメチル基、または置換基を有しても良いスルファモイル基を示す。
ただし、Ｒ^１〜Ｒ^４、および／または、Ｒ^１０〜Ｒ^１３の隣接した基は、一体となって、置換基を有してもよい芳香環を形成する。 As the quinophthalone yellow pigment, a quinophthalone yellow pigment represented by the following general formula (1) is particularly preferable from the viewpoint of high coloring power.
General formula (1)

[In General Formula (1), R ^{1 to} R ¹³ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. An aryl group which may have, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, phthalimidomethyl groups which may have a substituent, or substituents; The sulfamoyl group which may have is shown.
However, the adjacent groups of R ^{1 to} R ⁴ and / or R ^{10 to} R ¹³ together form an aromatic ring that may have a substituent.

  The preferred pigment ratio is 40 to 97% by weight of the metal halide phthalocyanine pigment and 3 to 60% by weight of the total amount of the yellow pigment, more preferably 60 to 97% by weight of the metal halide phthalocyanine pigment. The total amount is 3 to 40% by weight. In this range, weather resistance can be maintained and high brightness can be maintained.

  A preferable concentration of the pigment component in the present invention is 10 to 90% by weight, more preferably 15 to 85%, based on the total nonvolatile component of the coloring composition (100% by weight) from the viewpoint of obtaining sufficient color reproducibility. % By weight, most preferably 20-80% by weight. When the concentration of the pigment component is less than 10% by weight, sufficient color reproducibility cannot be obtained, and when it exceeds 90% by weight, the concentration of the pigment carrier is lowered and the stability of the coloring composition may be deteriorated. is there.

<Miniaturization of pigment>
The pigment used in the colored composition of the present invention can be refined by performing a salt milling treatment. The primary particle diameter of the pigment is preferably 20 nm or more because dispersibility in a colorant carrier such as a transparent resin and / or a solvent is good. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm. The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is obtained by approximating it to a cube of the obtained particle size, and the volume average particle size is defined as the average primary particle size.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight based on the total weight of the pigment (100% by weight) from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment (100% by weight).

<Dispersant>
The dispersant has a colorant affinity part that has the property of adsorbing to the colorant and a part that is compatible with the colorant carrier, and adsorbs to the colorant to stabilize dispersion of the colorant into the colorant carrier. It works to make it. Specific examples of the dispersant include amino group-containing acrylic block copolymers, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, and ammonium polycarboxylates. Salt, polycarboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, poly (lower alkylene imine) and reaction with polyester having free carboxyl group Oil-based dispersants such as amides and salts thereof, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic ester copolymers, styrene-maleic acid copolymers, polyvinyl Water-soluble resins such as alcohol and polyvinylpyrrolidone Compounds, polyester, modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more. Among these, an amino group-containing acrylic block copolymer is preferable.

As a commercially available product as a dispersant, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, manufactured by Big Chemie Japan, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, Or BYK-P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 139 manufactured by Nihon Lubrizol Co., Ltd., Lactimon, Lactimon-WS, or Bykumen et al. 0, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, manufactured by BASF, etc. , 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 50 0,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.
Examples of the amino group-containing acrylic block copolymer that can be suitably used include Disperbyk-2000 and 2001.

  When a dispersant is added, the total amount of the colorant (A) is based on 100% by weight, preferably 1 to 55% by weight, more preferably 5 to 45% by weight. When the blending amount of the dispersant is less than 1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion may be affected by an excessive dispersant.

<Photoacid generator (C)>
The photosensitive coloring composition of the present invention is characterized by containing a photoacid generator (C1) containing a triarylsulfonium compound. The photosensitive coloring composition of the present invention contains a photoacid generator (C1) containing a triarylsulfonium compound, thereby suppressing a decrease in lightness that occurs over time in an environment where a color filter is incorporated in a liquid crystal panel. can do. The inside of the liquid crystal panel sandwiched between two sheets of glass is an oxygen-blocking environment. In such an environment, the halogenated metal phthalocyanine green pigment is excited by ultraviolet rays and the like, and moisture contained in the photosensitive coloring matter Reacts and causes discoloration. Here, it is considered that the photoacid generator prevents the discoloration of the halogenated metal phthalocyanine-based green pigment by quenching the excited metal halide phthalocyanine. Since the triarylsulfonium compound-based photoacid generator has a planar structure, it has a strong interaction with the metal halide phthalocyanine having the planar structure, and a sufficient quenching effect can be obtained with a small amount of addition. Become.

Specific examples of triarylsulfonium compound-based photoacid generators include, but are not limited to, triphenylsulfonium chloride, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate ( And triphenylsulfonium trifluoromethanesulfonate), triphenylsulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, and triphenylsulfonium triflate.
Examples of commercially available products include WPAG-336, WPAG-367, WPAG-370, WPAG-469, and WPAG-638 manufactured by Wako Pure Chemical Industries, Ltd.

(Other photoacid generators)
Furthermore, one or two or more other photoacid generators can be used in combination with the triarylsulfonium compound photoacid generator. Other photoacid generators include triazine compounds, acetophenone derivative compounds, benzophenone compounds, halogen-containing compounds, sulfone compounds, diazomethane compounds, diazoketone compounds, sulfonic acid derivative compounds, sulfonimide compounds, phosphine oxides, thioxanthone compounds, Onium compound salts (excluding triarylsulfonium compounds).

  For example, as a triazine compound, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2- Phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (benzo [d] 1,3-dioxolan-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4, 6-bis (trichlorome L) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4- Dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine 2- (2-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-butoxystyryl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine, 2- (4-pentyloxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and the like.

  As acetophenone derivative compounds, acetophenone, methoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4-diphenoxydichloroacetophenone, diethoxyacetophenone, 1- (4- And isopropylphenyl) -2-hydroxy-2-methylpropan-1-one.

  Examples of the benzophenone compounds include benzophenone, 4-phenylbenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, diphenoxybenzophenone, and the like.

  As the halogen-containing compound, a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, or the like, preferably 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6- Bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine and the like can be mentioned.

  Examples of the sulfone compound include β-ketosulfone compounds and β-sulfonylsulfone compounds, preferably 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like.

  Diazomethane compounds include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis ( p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane, etc. It is done.

  Examples of the diazo ketone compound include 1,3-diketo-2-diazo compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like. The diazonaphthoquinone compound is an ester of 1,2-naphthoquinonediazide-4-sulfonic acid and 2,3,4,4′-tetrahydroxybenzophenone, 1,2-naphthoquinonediazide-4-sulfonic acid and 1,1, Esters with 1-tris (4-hydroxyphenyl) ethane, amides with 1,2-naphthoquinonediazide-4-sulfonic acid and diaminodiphenyl ether, 1,2-naphthoquinonediazide-5-sulfonic acid and 2,3,4 , 4′-tetrohydroxybenzophenone, methyl gallate, ester with 1,1,1-tris (4-hydroxyphenyl) ethane, diaminodiphenyl ether, and the like.

  As the sulfonic acid derivative compound, alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, imino sulfonate, etc., preferably benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, etc. Is mentioned.

  As sulfonimide compounds, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3 -Dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxyl Imido, N- (camphorsulfonyloxy Succinimide, N- (camphorsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane- 5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyl) Xyl) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7- Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2 , 3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimi N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7 -Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6- Oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (2-fluorophenylsulfonyloxy) phthalimide N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- ( -Fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide and the like.

  As phosphine oxides, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2,6-dichlorobenzoylphenylphosphine Oxide, 2,6-dimethoxyoxybenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Etc.

  Examples of the thioxanthone compound include 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, and the like.

  As onium compound salts, diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoro Antimonate, diphenyliodonium hexafluoroarsenate, bis (p- (1,1-dimethylethyl) phenyl) iodonium hexafluorophosphate, bis (p- (1,1-dimethylethyl) phenyl) iodonium mesylate, bis (p -(1,1-dimethylethyl) phenyl) iodonium Silate, bis (p- (1,1-dimethylethyl) phenyl) iodonium trifluoromethanesulfonate, bis (p- (1,1-dimethylethyl) phenyl) iodonium tetrafluoroborate, bis (p- (1,1-dimethyl) And ethyl) phenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, and triphenylsulfonium triflate.

The addition amount of the photoacid generator of the present invention is preferably 1% by weight to 4% by weight, more preferably 2% by weight to 3% by weight, based on the solid content of the photosensitive coloring composition. If the amount of the photoacid generator is too small, it is not possible to sufficiently suppress the decrease in brightness, and if added excessively, the initial decrease in brightness is caused.
In addition, solid content of the photosensitive coloring composition represents the component except volatile components, such as a solvent.

<Binder resin>
The binder resin is preferably a resin having a spectral 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.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin is preferably used in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

  Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of unsaturated ethylenic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

[Thermosetting compound]
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is a binder resin.

  Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, phenol compounds and / or resins, but the present invention is not limited thereto.

<Photopolymerizable monomer>
It is important that the green photosensitive coloring composition of the present invention contains a photopolymerizable monomer. The photopolymerizable monomer of the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more. The blending amount of the photopolymerizable monomer is preferably 5 to 400% by weight based on the total weight of the colorant (A) (100% by weight), and 10 to 10% from the viewpoint of photocurability and developability. More preferably, it is 300% by weight.

  Examples of the photopolymerizable monomer that is cured by ultraviolet rays or heat to produce a transparent resin include 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, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ester Terdi (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl ( Examples thereof include, but are not necessarily limited to, meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

(Polyfunctional photopolymerizable monomer having an acid group)
The colored composition of the present invention preferably has a polyfunctional photopolymerizable monomer having an acid group. Examples of the polyfunctional photopolymerizable monomer having an acid group include an esterified product of a poly (meth) acrylate containing a free hydroxyl group of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polycarboxylic acid And esterified products of monohydroxyalkyl (meth) acrylates. Specific examples include monomethyl oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. And monoesterified products containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. be able to. These polyfunctional photopolymerizable monomers can be used singly or as a mixture of two or more at any ratio as required.

  The content of the polyfunctional photopolymerizable monomer having an acid group is preferably 5 to 500 parts by weight and more preferably 20 to 300 parts by weight with respect to 100 parts by weight of the binder resin. When the amount is 5 parts by weight or more, the pixel strength or the smoothness of the pixel surface becomes better, and when the amount is 500 parts by weight or less, the alkali developability is excellent. This is preferable because there is no dirt or film residue.

  The acid value of the polyfunctional photopolymerizable monomer having an acid group is preferably 10 to 90 KOH-mg / g, and more preferably 20 to 50 KOH-mg / g. In the case of 10 KOH-mg / g or more, the alkali developability becomes better, and the residue other than the pixel formation portion can be reduced. When it is 90 KOH-mg / g or less, it is preferable because defective formation of pixels occurring in the alkali development step can be prevented.

<Photopolymerizable initiator>
The green photosensitive coloring composition of the present invention can contain a photopolymerizable initiator. The green photosensitive coloring composition of the present invention is cured by ultraviolet irradiation and has a role of forming a filter segment by a photolithographic method.

Examples of the photopolymerizable initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, -Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxypheny ) -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 (trichloromethyl) -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, or 2,4-trichloromethyl- ( 4′-methoxystyryl) -6-triazine or the like; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or Oxime ester compounds such as-(acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine Phosphine compounds such as oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds Compound; or titanocene compounds are used.
In particular, oxime ester compounds are preferred as the combination of the present invention.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the colorant (A) in the color filter coloring composition (100% by weight), and are photocurable and developable. From the viewpoint, it is more preferably 10 to 150% by weight.

<Sensitizer>
Furthermore, the green photosensitive coloring composition of the present invention can contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the colored composition (100% by weight). From the viewpoint of developability, it is more preferably 5 to 50% by weight.

<Solvent>
In the green photosensitive coloring composition of the present invention, the colorant (A) is sufficiently dispersed in a colorant carrier and applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to facilitate the formation of the filter segment, a solvent can be included. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, benzyl alcohol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3 -Butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m -Dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformua N-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert -Butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene Glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether Ter, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene group Cole monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone Emissions, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among them, glycols such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate have good dispersibility and solubility of the colorant (A) of the present invention. It is preferable to use ketones such as acetates and cyclohexanone and aromatic alcohols such as benzyl alcohol. A solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, the total weight of the colorant (A) is set to 800 to 4000 based on the total weight (100% by weight). It is preferably used in an amount of% by weight.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, a leveling agent is preferably added to the green photosensitive coloring composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, 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 Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the green photosensitive coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15% by weight based on the total amount of the thermosetting resin (100% by weight).

<Other additive components>
The green photosensitive coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the colorant (A) in the coloring composition (100% by weight).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant (A) in the coloring composition (100% by weight). .

<The manufacturing method of a coloring composition>
The green photosensitive coloring composition of the present invention is a mixture of a colorant (A), a dispersant, and a binder resin (C), and various types such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. The colorant (A) can be finely dispersed in a resin solvent solution using a dispersing means (pigment dispersion). The colored composition of the present invention can also be produced by mixing several types of colorants separately dispersed in a colorant carrier. The coloring composition can be prepared as a green coloring composition (resist material) for a solvent developing type or alkali developing type color filter. The coloring composition for a solvent developing type or alkali developing type color filter is prepared by adding a binder resin (C), a photopolymerizable initiator, a photopolymerizable monomer, an amino resin (F) to the pigment dispersion. Accordingly, other resins, solvents, dispersants, additives and the like can be mixed and adjusted. In addition, binder resin (C) is added with a coloring agent (A) and a dispersing agent at the time of pigment dispersion manufacture, and is contained in the green photosensitive coloring composition of this invention.

<Removal of coarse particles>
The colored composition of the present invention is mixed with 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 by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention is a color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one green filter segment is the color of the present invention. It is formed using the coloring composition for filters.

  The red filter segment can be formed using a normal red coloring composition containing a red pigment and a pigment carrier. Examples of the red coloring composition include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, Red pigments such as 281, 282, 283, 284, 285, 286, or 287 are used.

  The red coloring composition includes C.I. I. Pigment orange 43, 71, 73 or the like and / or 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, 181 182,185,187,188,193,194,198,199,213, or may be used in combination of a yellow pigment 214, and the like.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a pigment carrier. Examples of the blue coloring composition include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, Blue pigments such as 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 are used. .

  The blue coloring composition includes C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, Purple pigments such as 37, 39, 42, 44, 47, 49, and 50 can be used in combination.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method. The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. 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.

  When forming a filter segment by a photolithography method, a coating composition such as spray coating, spin coating, slit coating, roll coating, or the like is applied to the transparent composition on the transparent composition prepared as the solvent developing type or alkali developing type coloring resist. To apply a dry film thickness of 0.2 to 5 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 alkali developer or spraying the developer by spraying 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, 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.

  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, a water-soluble or alkaline water-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.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. 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 substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the liquid crystal display panel can be further increased. Examples of the black matrix include, but are not limited to, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, and a resin film in which a light-shielding agent is dispersed. 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.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the following, “parts” means “parts by weight” and “%” means “% by weight” unless otherwise specified.

(Average molecular weight)
The weight average molecular weight (Mw) is a polystyrene-equivalent number average measured using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. Molecular weight (Mn) and weight average molecular weight (Mw).

(Acid value)
The acid value is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K 0070.

<Manufacture of refined pigments>
(Production of green refined pigment (PG-1))
Green pigment C.I. I. 500 parts of Pigment Green 58 (“First Gain Green A110” manufactured by DIC Corporation), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded 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, a green refined pigment (PG-1) was obtained. The obtained pigment had a volume average primary particle size of 25 nm.

(Manufacture of yellow refined pigment (PY-1))
Quinophthalone yellow pigment C.I. I. Pigment Yellow 138 (BASF “Pariol Yellow K0960-HD”) 500 parts, sodium chloride 2500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 100 ° C. for 6 hours. did. 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, a yellow refined pigment (PY-1) was obtained. The obtained pigment had a volume average primary particle size of 26 nm.

(Manufacture of yellow refined pigment (PY-2))
Compound (1) was obtained according to the synthesis method described in JP-A-2008-81666.
Compound (1)

To 300 parts of methyl benzoate, 100 parts of compound (1), 70 parts of 2,3-naphthalenedicarboxylic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the quinophthalone compound (a) and the disappearance of the starting compound (1) were confirmed by TOF-MS. Further, after cooling to room temperature, the reaction mixture was added to 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 120 parts of quinophthalone compound (a). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (a).
Quinophthalone compound (a)

  70 parts of quinophthalone compound (a), C.I. I. 30 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 2 (PY-2) were obtained. The average primary particle size was 30.4 nm.

(Manufacture of yellow refined pigment (PY-3))
Compound (2) was obtained according to the synthesis method described in JP-A-2008-81666.
Compound (2)

To 300 parts of methyl benzoate, 100 parts of compound (2), 108 parts of tetrachlorophthalic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the quinophthalone compound (b) and the disappearance of the starting compound (2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol, and dried to obtain 120 parts of a quinophthalone compound (b). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (b).
Quinophthalone compound (b)

  Subsequently, 100 parts of the obtained quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of a yellow colorant (PY-3) were obtained. The average primary particle size was 31.1 nm.

(Yellow colorant (PY-4)
To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic anhydride and 154 parts of benzoic acid were added, heated to 180 ° C., and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture was added to 5440 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 116 parts of quinophthalone compound (c). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (c).
Quinophthalone compound (c)

  Subsequently, 100 parts of the obtained quinophthalone compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of yellow colorant 3 (PY-4) were obtained. The average primary particle size was 34.1 nm.

<Preparation of acrylic resin solution 1>
A resin type dispersant (“Ajisper PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.) was diluted with propylene glycol monomethyl ether acetate to prepare an acrylic resin solution 1 having a solid content of 30%.

<Method for producing colored composition>
(Production of green pigment dispersion (A-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a colorant dispersion (DG-1) was produced.
Green colorant (PG-1): 12.0 parts Resin type dispersant: 1.0 part ("EFKA4300" manufactured by BASF)
Acrylic resin solution 1: 35.0 parts Solvent: 52.0 parts Propylene glycol monomethyl ether acetate (PGMAC)

<Production of pigment dispersion B>
(Production of yellow pigment dispersion (B-1))
10.0 parts of yellow refined pigment (PY-1), 6.7 parts of resin type dispersant (“EFKA4300” manufactured by BASF), 26.7 parts of acrylic resin solution, and 23.4 of propylene glycol monomethyl ether acetate Part of the mixture was stirred and mixed uniformly with a disper, and then using a zirconia bead having a diameter of 0.5 mm and using an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) as a media type wet disperser for 4 hours. After the dispersion, 33.2 parts of propylene glycol monomethyl ether acetate was added to obtain a yellow pigment dispersion (B-1).

(Production of yellow pigment dispersions B-2, B-3, B-4)
The yellow pigment dispersion (B-2) and (B-3) were the same as (Production of yellow pigment dispersion (B-1)) except that the yellow refined pigment was changed to (PY-2, 3, 4). ) And (B-4) were obtained.

<Preparation of green photosensitive coloring composition>
In the composition and blending amount (parts by weight) shown in Table 1, the pigment dispersion, the photoacid generator, the acrylic resin solution, the photopolymerizable monomer, the photopolymerization initiator, the additive, The mixture with the solvent was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain each colored resist material.

<Evaluation of green photosensitive coloring composition>
The lightness difference before and after the weather resistance test of the obtained photosensitive coloring composition was evaluated by the following method. The results are shown in Table 1.

[Weather resistance test]
Assuming the actual operating environment of the color filter, a light resistance test was conducted using an alternative evaluation device capable of forming an oxygen barrier environment. (Figure 1)
(Method for producing substrate for weather resistance test)
The obtained photosensitive coloring composition was applied to a 10 cm × 10 cm glass substrate by a spin coating method, and then the solvent was removed with a vacuum dryer to obtain a photosensitive coloring composition film. Next, the substrate was exposed to ultraviolet rays through a blue plate having a thickness of 1 nm using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 40 minutes in a clean oven. Next, the post-baked substrate was again coated with an overcoat agent by the spin cord method, and then dried using a vacuum dryer. Thereafter, the substrate was baked on a hot plate at 90 ° C. for 2 minutes, and further heated in a green oven at 230 ° C. for 60 minutes. Next, the obtained colored composition film and the substrate with the overcoat agent were cut at 2 cm × 5 cm. After dripping 0.020 ml of UV curable sealant on the cut substrate coating, it was covered with an 18 mm × 18 mm cover glass and left in a horizontal state until it spreads over the edge of the cover glass. Thereafter, the sealed portion of the cut substrate was exposed to ultraviolet light at an exposure amount of 4000 mJ / cm ² using an ultra-high pressure mercury lamp to obtain a weather resistance test substrate. (Figure 1)

(Weather resistance evaluation method)
The initial brightness in the XYZ color system of the substrate for weather resistance test is measured. An LED backlight was installed in a high-temperature and high-humidity oven (65 ° C./90% RH), the film surface was placed on the backlight, and the above-mentioned weather resistance test substrate was arranged. Take out at about 72 h, and measure the brightness again at the same location as the initial brightness measurement. The brightness is defined as the post-irradiation brightness. The calculation formula and rank of the brightness change rate are described as follows.
[Brightness change rate calculation formula:]
Lightness change rate = (lightness after irradiation−initial lightness) / initial lightness ○: −8.0% <lightness change rate <0.0%
Δ: -15.0% <lightness change rate <-8.0%
X: -30.0% <lightness change rate <-15.0%

Abbreviations in Table 1 are shown below.
Pigment dispersion: A-1
Photoacid generator (C1-1):
"Triphenylsulfonium bromide" manufactured by Tokyo Chemical Industry Co., Ltd.
(Photoacid generator containing triarylsulfonium compound)
Photoacid generator (C1-2):
“WPAG-367: (diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate)” manufactured by Wako Pure Chemical Industries, Ltd.
(Photoacid generator containing triarylsulfonium compound)
Photoacid generator (C2-1):
"Trimethylsulfonium iodide" manufactured by Tokyo Chemical Industry Co., Ltd.
(Photoacid generator containing no triarylsulfonium compound)
-Acrylic resin solution-Photopolymerizable monomer: Dipentaerythritol penta and hexaacrylate ("M402" manufactured by Toa Gosei)
Photopolymerization initiator: ("Irgacure 369E" manufactured by BASF)
Additive: Trimethylolpropane tris (3-mercaptobutyrate) (“TPMB” manufactured by Showa Denko KK)
Organic solvent A: Propylene glycol monomethyl ether acetate Organic solvent B: Ethyl 3-ethoxypropionate

  As shown in Table 1, in Examples 1 to 12, with respect to the green pigment dispersion, by adding a photoacid generator (C1) containing a triarylsulfonium compound, the lightness change rate of the photosensitive coloring composition film is It was (triangle | delta) or (circle), and with respect to Comparative Examples 1-3, the brightness change rate improved, without the big fall in initial brightness. In Example 1, when the amount of the photoacid generator (C1) containing a triarylsulfonium compound was large, the lightness change rate improved, but the initial lightness decreased. In Comparative Example 2, when the photoacid generator (C2) containing no triarylsulfonium compound was added, no improvement in brightness change rate was observed.

1: Cover glass 2: UV curable sealant 3: Overcoat agent 4: Photosensitive coloring composition film 5: Glass substrate 6: Backlight

Claims (5)

  A photosensitive coloring composition comprising a halogenated metal phthalocyanine (A), a quinophthalone yellow pigment (B) and a photoacid generator (C), wherein the halogenated metal phthalocyanine (A) comprises a halogenated copper phthalocyanine, a halogenated A photosensitive coloring composition for a color filter, which is at least one selected from zinc phthalocyanine and halogenated aluminum phthalocyanine, wherein the photoacid generator (C) contains a triarylsulfonium compound (C1).   2. The photosensitive color for color filter according to claim 1, wherein the content of the photoacid generator (C) is from 1% by weight to 4% by weight in the total solid content of the photosensitive coloring composition. Composition. The photosensitive coloring composition for color filters according to claim 1 or 2, wherein the quinophthalone yellow pigment (B) is a quinophthalone yellow pigment represented by the following general formula (1).
General formula (1)

[In General Formula (1), R ^{1 to} R ¹³ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. An aryl group which may have, —SO ₃ H; —COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts, phthalimidomethyl groups which may have a substituent, or substituents; The sulfamoyl group which may have is shown.
However, the adjacent groups of R ^{1 to} R ⁴ and / or R ^{10 to} R ¹³ together form an aromatic ring which may have a substituent. ]   The photosensitive coloring composition for a color filter according to any one of claims 1 to 3, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.   A color filter comprising a color filter segment formed from the photosensitive coloring composition for a color filter according to claim 1 on a substrate.

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