JP6864567B2 - Photosensitive coloring compositions and color filters for color filters - Google Patents

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 by using the photosensitive coloring composition. ..

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 having a photomask, developing the mixture to dissolve and remove an unexposed portion, and then post-baking the mixture (for example, Patent Document 1). , Patent Document 2) is known.

Liquid crystal display elements equipped with such color filters are required to have high brightness and an expansion of the color reproduction area. Therefore, color filters are also 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-based yellow pigment composition is known as a material capable of providing a color filter having high brightness and a wide color reproduction range. (See, for example, Patent Document 3). However, green pixels formed by combining a pigment composition containing a metal halide phthalocyanine pigment and a quinophthalone-based yellow pigment composition are LED backlights in an oxygen-blocking environment such as those incorporated in a liquid crystal panel. In this case, there is a problem that the brightness of the green pixel decreases with time under the condition of constant temperature and humidity (65 ° C./95%). (Hereafter referred to as weather resistance.)

Japanese Unexamined Patent Publication No. 2-144502 Japanese Unexamined Patent Publication No. 3-53201 JP-A-2007-284589 Japanese Unexamined Patent Publication No. 2010-250225 JP-A-2009-35671

An object of the present invention is to provide a photosensitive coloring composition having good weather resistance and capable of forming green pixels that maintain high brightness. A further object of the present invention is to provide a color filter including green pixels formed from the photosensitive coloring composition, and a color liquid crystal display element including the color filter.

As a result of intensive research to solve the above problems, the present inventors have conducted diligent research.
It has been found that a photosensitive coloring composition containing a metal halide phthalocyanine (A), a quinophthalone-based yellow pigment (B) and a photoacid generator (C) has excellent weather resistance.

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

The present invention also relates to the above-mentioned photosensitive coloring composition for a color filter, wherein the content of the photoacid generator (C) is 1 to 4% by weight based on 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-mentioned photosensitive coloring composition for a color filter, wherein the quinophthalone-based yellow pigment (B) is a quinophthalone-based yellow pigment represented by the following general formula (1).
General formula (1)

[In the general formula (1), R ^{1 to} R ¹³ independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. which may have an aryl group, -SO 3 _H; -COOH; and monovalent to trivalent metal salt thereof acidic groups, alkyl ammonium salts, which may have a substituent phthalimidomethyl group, or a substituent Indicates a sulfamoyl group that may have.
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-mentioned coloring 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 characterized in that a filter segment formed of the green photosensitive coloring composition is provided on a substrate.

By using the photosensitive coloring composition of the present invention, it is possible to form green pixels having good weather resistance and high brightness. Therefore, a color filter including green pixels formed by using the photosensitive coloring composition of the present invention is, for example, a transmissive or reflective color liquid crystal display element, a color image pickup tube element, a color sensor, and an organic EL display. It is extremely useful for elements, electronic paper, etc.

The schematic which shows the weather resistance test method.

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

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

A typical halogenated copper phthalocyanine pigment is represented by a color index (CI) number. I. Pigment Green 36, C.I. I. Pigment Green 7 etc. can be mentioned.

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

As the metal halide phthalocyanine (A), other green pigments that can be used in combination with the zinc halide phthalocyanine pigment include C.I. I. Pigment Green 7, 10, 36, 37, aluminum phthalocyanine pigments and the like described in Japanese Patent No. 4893859 and the like can be mentioned. Of these, C.I. I. Pigment Green 7C. I. Pigment Green 36, or the aluminum phthalocyanine pigment described in Japanese Patent No. 4893859 and the like.

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

<Kinophthalone yellow pigment (B)>
Examples of the quinophthalone-based 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。 Further, as the quinophthalone-based yellow pigment, a quinophthalone-based yellow pigment represented by the following general formula (1) is particularly preferable in terms of high coloring power.
General formula (1)

[In the general formula (1), R ^{1 to} R ¹³ independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. which may have an aryl group, -SO 3 _H; -COOH; and monovalent to trivalent metal salt thereof acidic groups, alkyl ammonium salts, which may have a substituent phthalimidomethyl group, or a substituent Indicates a sulfamoyl group that may have.
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 preferable ratio of the pigment 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, and more preferably 60 to 97% by weight of the metal halide phthalocyanine pigment and the yellow pigment. The total amount is 3-40% by weight. In this range, weather resistance can be maintained and high brightness can be maintained.

In the present invention, the concentration of the pigment component is preferably 10 to 90% by weight, more preferably 15 to 85%, based on the total non-volatile components of the coloring composition (100% by weight) from the viewpoint of obtaining sufficient color reproducibility. It is% by weight, most preferably 20 to 80% by weight. If the concentration of the pigment component is less than 10% by weight, sufficient color reproducibility cannot be obtained, and if it exceeds 90% by weight, the concentration of the pigment carrier becomes low and the stability of the coloring composition may deteriorate. is there.

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

Salt milling is a machine in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is heated by a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a 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 acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

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 price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, most preferably 300 to 1000% by weight, based on the total weight of the pigment (100% by weight).

The water-soluble organic solvent has a function of wetting 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 used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. 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, most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

When the pigment is subjected to salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the 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-affinitive portion having a property of adsorbing to the colorant and a portion compatible with the colorant carrier, and adsorbs to the colorant to stabilize the dispersion of the colorant on the colorant carrier. It works to change. Specifically, as the dispersant, an amino group-containing acrylic block copolymer, polyurethane, polycarboxylic acid ester such as polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, ammonium polycarboxylic acid. Reaction of salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products of these, poly (lower alkyleneimine) with polyesters having free carboxyl groups. Oily dispersants such as amides and salts thereof formed by, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl Water-soluble resins such as alcohol and polyvinylpyrrolidone, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphoric acid ester-based, etc. are used, and these are used alone or in admixture of two or more. Can be used. Of these, an amino group-containing acrylic block copolymer is preferable.

As a dispersant, commercially available products include 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 Lactimon, Lactimon-WS or Bykuman, etc., SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, manufactured by Japan Lubrizol. , 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. , PB822, PB824 and the like.
Examples of the amino group-containing acrylic block copolymers that can be preferably used as described above include Disperbyk-2000 and 2001.

When the dispersant is added, the total amount of the colorant (A) is used as a reference (100% by weight), preferably 1 to 55% by weight, and more preferably 5 to 45% by weight. If the blending amount of the dispersant is less than 1% by weight, it is difficult to obtain the effect of addition, and if the blending amount is more than 55% by weight, the dispersion may be affected by the excess 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 to suppress a decrease in brightness that occurs over time in an environment in which a color filter is incorporated in a liquid crystal panel. can do. The inside of the liquid crystal panel sandwiched between two pieces of glass is an oxygen-blocking environment, and in such an environment, the metal halide phthalocyanine-based green pigment becomes an excited state due to ultraviolet rays, etc. It reacts and causes discoloration. Here, it is considered that the photoacid generator prevents the metal halide phthalocyanine-based green pigment from being discolored by quenching the excited metal phthalocyanine halide. Since the triarylsulfonium compound-based photoacid generator has a planar structure, it has a strong interaction with the metal halide phthalocyanine, which also has a planar structure, and it is possible to obtain a sufficient quenching effect with a small amount of addition. Become.

Specific examples of the triarylsulfonium compound-based photoacid generator are not limited to the following, but are limited to triphenylsulfonium chloride, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium trifluoromethanesulfonate (triphenylsulfonium trifluoromethanesulfonate). Triphenylsulfonium trifluoromethanesulfonate), triphenylsulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate, and triphenylsulfonium triflate.
Examples of commercially available products include WPAG-336, WPAG-376, WPAG-370, WPAG-469, and WPAG-638 manufactured by Wako Pure Chemical Industries, Ltd.

(Other photoacid generators)
Further, one or more other photoacid generators can be used in combination with the triarylsulfonium compound-based 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, etc. Examples include onium compound salts (excluding triarylsulfonium compounds).

For example, as triazine compounds, 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 (trichloromethyl) -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-butoxystylyl) -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-methylpropane-1-one, 1-hydroxycyclohexylphenylketone, 4-diphenoxydichloroacetophenone, diethoxyacetophenone, 1- (4- (4-) Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one and the like can be mentioned.

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

Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound, preferably 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane and 2-phenyl-4,6-. Examples thereof include bis (trichloromethyl) -s-triazine and 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine.

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

As diazomethane compounds, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-kisilylsulfonyl) diazomethane, bis ( p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane, etc. Be done.

Examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound and the like. The diazonaphthoquinone compound is an ester of 1,2-naphthoquinone diazide-4-sulfonic acid and 2,3,4,4'-tetrahydroxybenzophenone, and 1,2-naphthoquinone diazide-4-sulfonic acid and 1,1, Ester with 1-tris (4-hydroxyphenyl) ethane, amide with 1,2-naphthoquinone diazide-4-sulfonic acid and diaminodiphenyl ether, etc., 1,2-naphthoquinone diazide-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.

Examples of the sulfonic acid derivative compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates and the like, preferably benzointosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate and the like. Can be mentioned.

As sulfonimide compounds, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [ 2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-en-2,3 -Dicarboxyimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthyldicarboxyl Imide, N- (camfersulfonyloxy) succinimide, N- (campfarsulfonyloxy) phthalimide, N- (campfarsulfonyloxy) diphenylmaleimide, N- (campfarsulfonyloxy) bicyclo [2.2.1] hept-5-ene -2,3-dicarboxyimide, N- (campharsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (camphasulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxyimide, N- (camfersulfonyloxy) naphthyldicarboxyimide, N- (4-methylphenylsulfonyloxy) succinimide, N- ( 4-Methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxyimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) Bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) naphthyldicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) ) Succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimi Do, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) -7 -Oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6- Oxy-2,3-dicarboxymid, N- (2-trifluoromethylphenylsulfonyloxy) naphthyldicarboxyimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (2-fluorophenylsulfonyloxy) phthalimide , N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4) -Fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] Examples thereof include heptane-5,6-oxy-2,3-dicarboxyimide and N- (4-fluorophenylsulfonyloxy) naphthyldicarboxyimide.

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-dimethitoxybenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide And so on.

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 pyrene sulfonate, diphenyliodonium dodecylbenzene sulfonate, 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 tosylate, bis (p- (1,1-dimethylethyl) phenyl) iodonium trifluoromethanesulfonate, bis (p- (1,1-dimethylethyl) phenyl) iodonium tetra Fluorobolate, bis (p- (1,1-dimethylethyl) phenyl) iodonium chloride, bis (p-chlorophenyl) iodonium chloride, bis (p-chlorophenyl) iodonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, Examples include triphenylsulfonium triflate.

The amount of the photoacid generator added in 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, the decrease in brightness cannot be sufficiently suppressed, and if it is added excessively, the decrease in brightness at the initial stage is caused.
The solid content of the photosensitive coloring composition represents a component excluding 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 preferably disperse the colorant. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the Mw / Mn value is preferably 10 or less.

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

Since the binder resin has good film forming properties and various resistances, it is preferable to use the binder resin in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant, 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, and polyvinyl acetate. , Polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like. .. Above all, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include a resin having an acidic group such as a carboxyl group and a sulfone group. Specifically, the alkali-soluble resin includes an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Isobutylene / (maleic anhydride) maleic anhydride copolymer and the like can be mentioned. Among them, an acrylic resin having an acidic group and at least one resin selected from 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 a resin in which an unsaturated ethylenically double bond is introduced by the methods (i) and (ii) shown below.

[Method (i)]
As the method (i), for example, the side chain epoxy group of the copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group with one or more other monomers is used. , The carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenically double bond is added and reacted, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an unsaturated ethylenically double bond and a carboxyl group. There is a way to introduce it.

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

Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyls, halogens, nitros, and cyano substituents. Examples thereof include monocarboxylic acids, which may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic dianhydride such as trimellitic dianhydride may be used, or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used to obtain the remaining anhydride. The group can also be hydrolyzed. Further, when etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenically double bond is used as the polybasic acid anhydride, the unsaturated ethylenically double bond can be further 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 with one or more other monomers. There is a method of introducing an unsaturated ethylenically double bond and a carboxyl group by adding an unsaturated ethylenic monomer having an epoxy group to a part of the carboxyl group.

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

Examples of the unsaturated ethylenic monomer 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 and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited thereto. However, two or more types can be used together.

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

Thermosetting compounds include, for example, 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, but are not limited to, urea compounds and / or resins, phenolic compounds and / or resins.

<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 contains a monomer or oligomer that is cured by ultraviolet rays, heat, or the like 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 is 10 to 10% from the viewpoint of photocurability and developability. More preferably, it is 300% by weight.

Examples of the photopolymerizable monomer that cures with ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl ( Meta) 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 Glycoldi (meth) acrylate, trimethylolpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A di Glycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, Various acrylic acid esters such as (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and methacrylic acid ester of methylolated melamine, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, Examples thereof include, but are not limited to, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

(Polyfunctional photopolymerizable monomer having an acid group)
The coloring 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 free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid. And an esterified product of monohydroxyalkyl (meth) acrylates and the like. Specific examples include monohydroxyoligoacrylates such as trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, or monohydroxyoligomethacrylates. Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, oxalic acid, glutaric acid, and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2- Examples thereof include monohydroxymonoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates. These polyfunctional photopolymerizable monomers may be used alone or in admixture of two or more at any ratio, if necessary.

The content of the polyfunctional photopolymerizable monomer having an acid group is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts by weight, based on 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. It 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, more preferably 20 to 50 KOH-mg / g. When it is 10 KOH-mg / g or more, the alkali developability becomes better and the residue other than the pixel forming portion can be reduced. When it is 90 KOH-mg / g or less, it is preferable because it is possible to prevent poor pixel formation that occurs in the alkaline development step.

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

Examples of the photopolymerizable initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- Acetphenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin, Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4 Benzophenone compounds such as'-methyldiphenylsulfide or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, Thioxanthone compounds such as 4-diisopropylthioxanthone or 2,4-diethylthioxanthone; 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 (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4 Triazine compounds such as -trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxy) M)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate compounds; A carbazole-based compound; an imidazole-based compound; or a titanosen-based compound or the like is used.
In particular, an oxime ester compound is preferable as a combination of the present invention.

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

<Sensitizer>
Further, the green photosensitive coloring composition of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycolate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3', or 4,4' -Tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizers described in "Special Functional Materials" (1986, CMC) can be mentioned, but are not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

Two or more sensitizers may be used in any ratio as required. When the sensitizer is used, the blending amount is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the coloring composition (100% by weight), and is photocurable. 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 the colorant carrier and coated on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. A solvent can be included to facilitate the formation of the filter segment. 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, and the like. 2-Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3 -Butandiol, 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-dimethylformamide, 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 monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, 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 Recall 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, methyl cyclohexanol, acetic acid Examples thereof include n-amyl, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like.

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

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

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes 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 polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane 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 to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the green photosensitive coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. Phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective as the curing agent, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. 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 amidin compounds and salts thereof (eg, eg). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6, etc.) -Methacryloxyethyl-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.) and the like 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 ingredients>
The green photosensitive coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to improve the adhesion with the transparent substrate.

Examples of the storage stabilizer include quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. 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).

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and 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-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as 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). ..

<Manufacturing method of 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 to produce the colorant (pigment dispersion). Further, the coloring composition of the present invention can also be produced by mixing several kinds of coloring agents separately dispersed in a coloring agent 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. A coloring composition for a solvent-developed or alkaline-developed color filter requires a binder resin (C), a photopolymerizable initiator, a photopolymerizable monomer, and an amino resin (F) in the pigment dispersion. Other resins, solvents, dispersants, additives and the like can be mixed and adjusted accordingly. The binder resin (C) is added together with the colorant (A) and the dispersant at the time of producing the pigment dispersion, and is contained in the green photosensitive coloring composition of the present invention.

<Removal of coarse particles>
The coloring composition of the present invention was mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, by means such as centrifugation, sintering filter, and membrane filter. It is preferable to remove dust. As described above, it is preferable that the coloring composition does not substantially contain particles having a size of 0.5 μm or more. 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 including at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and at least one green filter segment is the color of the present invention. It is formed by using a coloring composition for a filter.

The red filter segment can be formed using a conventional red coloring composition containing a red pigment and a pigment carrier. The red coloring composition includes, for example, 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.

Further, the red coloring composition includes C.I. I. Pigment Orange 43, 71, or 73 and other orange pigments 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, Yellow pigments such as 193, 194, 198, 199, 213, or 214 can be used in combination.

The blue filter segment can be formed using a conventional blue coloring composition containing a blue pigment and a pigment carrier. The blue coloring composition includes, for example, 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. ..

Further, 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.

<Manufacturing method of color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as the printing ink, and therefore, as a manufacturing method of the color filter, it is excellent in mass productivity at low cost. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

When forming a filter segment by a photolithography method, a method of applying a coloring composition prepared as the solvent-developing type or alkali-developing type coloring resist on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. Therefore, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without 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 manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the ultraviolet exposure sensitivity, the colored resist was applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin was applied and dried to form a film for preventing polymerization inhibition by oxygen. After that, ultraviolet exposure can also be performed.

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 methods, but the coloring composition of the present invention can be used in any of the methods. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. 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 the filter segment is transferred to a desired substrate.

If a 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 enhanced. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but the black matrix is not limited thereto. Further, 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 thereafter. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the brightness can be improved.

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

(Average molecular weight)
The weight average molecular weight (Mw) is a polystyrene-equivalent number average measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120 GPC) equipped with an RI detector and 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 solid content in accordance with the potentiometric titration method of JIS K 0070.

<Manufacturing of refined pigments>
(Manufacturing of green refined pigment (PG-1))
Green pigment C.I. I. Pigment Green 58 (“First Gane Green A110” manufactured by DIC Corporation), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. Then, a green micronization-treated pigment (PG-1) was obtained. The volume average primary particle size of the obtained pigment was 25 nm.

(Manufacture of Yellow Micronized Pigment (PY-1))
Kinoftalone yellow pigment C.I. I. Pigment Yellow 138 (BASF's "Pariotor Yellow K0960-HD") 500 parts, sodium chloride 2500 parts, and diethylene glycol: 250 parts are charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C for 6 hours. did. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. Then, a yellow micronized pigment (PY-1) was obtained. The volume average primary particle size of the obtained pigment was 26 nm.

(Manufacture of Yellow Micronized Pigment (PY-2))
Compound (1) was obtained according to the synthesis method described in JP-A-2008-81566.
Compound (1)

To 300 parts of methyl benzoate, 100 parts of compound (1), 70 parts of 2,3-naphthalenedicarboxylic acid anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. By TOF-MS, the formation of the quinophthalone compound (a) and the disappearance of the raw material compound (1) were confirmed. Further, after cooling to room temperature, the reaction mixture was added to 3130 parts of acetone, and the mixture was 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).
Kinoftalone compound (a)

70 parts of quinophthalone compound (a), C.I. I. Pigment Yellow 138 (BASF's "Pariotor Yellow K0960-HD"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was put into warm water and stirred for 1 hour while heating at about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. 97 parts of yellow colorant 2 (PY-2) was obtained. The average primary particle size was 30.4 nm.

(Manufacture of Yellow Micronized Pigment (PY-3))
Compound (2) was obtained according to the synthesis method described in JP-A-2008-81566.
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. By TOF-MS, the formation of the quinophthalone compound (b) and the disappearance of the raw material compound (2) were confirmed. Further, 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 quinophthalone compound (b). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (b).
Kinoftalone compound (b)

Subsequently, 100 parts of the obtained quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was put into warm water and stirred for 1 hour while heating at about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. 98 parts of yellow colorant (PY-3) was 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 acid 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 the mixture was stirred at room temperature for 1 hour. The product was filtered off, 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).
Kinoftalone compound (c)

Subsequently, 100 parts of the obtained quinophthalone compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was put into warm water and stirred for 1 hour while heating at about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. 97 parts of yellow colorant 3 (PY-4) was obtained. The average primary particle size was 34.1 nm.

<Adjustment 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%.

<Manufacturing method of coloring composition>
(Manufacture of Green Pigment Dispersion (A-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours 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. The colorant dispersion (DG-1) was prepared by filtering with the filter of.
Green colorant (PG-1): 12.0 parts Resin type dispersant: 1.0 parts (BASF "EFKA4300")
Acrylic resin solution 1: 35.0 parts Solvent: 52.0 parts Propylene glycol monomethyl ether acetate (PGMAC)

<Pigment dispersion B production>
(Manufacture of Yellow Pigment Dispersion (B-1))
10.0 parts of yellow micronized pigment (PY-1), 6.7 parts of resin type dispersant (BASF "EFKA4300"), 26.7 parts of acrylic resin solution, and 23.4 parts of propylene glycol monomethyl ether acetate. After uniformly stirring and mixing the mixture of parts with a disper, using zirconia beads having a diameter of 0.5 mm and using an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) as a media type wet disperser for 4 hours. After dispersion, 33.2 parts of propylene glycol monomethyl ether acetate was added to obtain a yellow pigment dispersion (B-1).

(Manufacture of Yellow Pigment Dispersions B-2, B-3, B-4)
The yellow pigment dispersions (B-2) and (B-3) are the same as in (Production of yellow pigment dispersion (B-1)) except that the yellow pigments have been changed to (PY-2, 3, 4). ), (B-4) were obtained.

<Preparation of green photosensitive coloring composition>
Pigment dispersions, photoacid generators, acrylic resin solutions, photopolymerizable monomers, photopolymerization initiators, additives, and the like, with the composition and blending amount (parts by weight) as shown in Table 1. The mixture with the solvent was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain each colored resist material.

<Evaluation of green photosensitive coloring composition>
The difference in brightness 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, the light resistance test was conducted using an alternative evaluation device that can form an oxygen blocking environment. (Fig. 1)
(Method of manufacturing a substrate for weather resistance test)
The obtained photosensitive coloring composition was applied to a glass substrate of 10 cm × 10 cm by a spin coating method, and then the solvent was blown off by a vacuum dryer to obtain a photosensitive coloring composition film. Next, this substrate was exposed to ultraviolet rays through a 1 nm-thick blue plate using an ultra-high pressure mercury lamp. Then, this substrate was spray-developed with an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C. for 40 minutes. Then, the post-baked substrate was again coated with an overcoating agent by a spin cord method, and then dried using a vacuum dryer. Then, the substrate was fired on a hot plate at 90 ° C. for 2 minutes, and then further heated in a green oven at 230 ° C. for 60 minutes. Next, the obtained colored composition film and the substrate with the overcoating agent were cut into 2 cm × 5 cm. After 0.020 ml of an ultraviolet curing sealant was dropped onto the cut substrate coating film, a cover glass of 18 mm × 18 mm was covered, and the mixture was allowed to stand in a horizontal state until it spreads on the edge of the cover glass. Then, the sealed portion of the cut substrate was ^{exposed to ultraviolet rays with an exposure amount of 4000 mJ / cm 2} using an ultra-high pressure mercury lamp to obtain a weather resistance test substrate. (Fig. 1)

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

The 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):
Wako Pure Chemical Industries, Ltd. "WPAG-376: (diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate)"
(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 (Toagosei "M402")
-Photopolymerization initiator: (BASF's "Irgacure 369E")
-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, the rate of change in brightness of the photosensitive coloring composition film was increased by adding a photoacid generator (C1) containing a triarylsulfonium compound with respect to the green pigment dispersion. It was Δ or ◯, and the rate of change in brightness was improved without a significant decrease in initial brightness as compared with Comparative Examples 1 to 3. In Example 1, when the amount of the photoacid generator (C1) containing the triarylsulfonium compound was large, the rate of change in brightness was improved, but the initial brightness was decreased. In Comparative Example 2, when the photoacid generator (C2) containing no triarylsulfonium compound was added, the rate of change in brightness was not improved.

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

Claims (4)

Photosensitive coloring containing metal halide phthalocyanine (A), quinophthalone-based yellow pigment (B) , photopolymerizable monomer, photopolymerization initiator and metal halide phthalocyanine (A) photoacid generator (C) for quenching. In the composition, the metal halide phthalocyanine (A) is at least one selected from copper halide phthalocyanine, zinc halide phthalocyanine, and aluminum halide phthalocyanine, and the photoacid generator (C) is triaryl. A photosensitive coloring composition for a color filter, which comprises a sulfonium compound (C1). The photosensitive coloring for a color filter according to claim 1, wherein the content of the photoacid generator (C) is 1% by weight or more and 4% by weight or less in the total solid content of the photosensitive coloring composition. Composition. The photosensitive coloring composition for a color filter according to claim 1 or 2, wherein the quinophthalone-based yellow pigment (B) is a quinophthalone-based yellow pigment represented by the following general formula (1).
General formula (1)

[In the general formula (1), R ^{1 to} R ¹³ independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. which may have an aryl group, -SO 3 _H; -COOH; and monovalent to trivalent metal salt thereof acidic groups, alkyl ammonium salts, which may have a substituent phthalimidomethyl group, or a substituent Indicates a sulfamoyl group that may have.
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. ] On a substrate, a color filter characterized by comprising comprises a color filter segments made formed from the color filter photosensitive coloring composition according to any one of claims 1-3.

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