JP2011253152A - Photosensitive coloring agent, and color filter using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring agent that does not generate foreign substances even if it is a thick film, has high resolution, and has such excellent adhesion as to cause no pattern peeling, and to provide a color filter suitable for COA system using the photosensitive coloring agent.SOLUTION: The photosensitive coloring agent includes a coloring agent (A), a resin (B), and photopolymerizable monomer (C), a photopolymerization initiator (D) including at least one kind of compound selected from a group consisting of an acetophenone compound, an acylphosphine oxide compound, and an oxime compound, and a sensitizer (E) containing a compound having a specific structure. The content of the photopolymerization initiator (D) is 3-20 wt.% based on 100 wt.% of the total solid component of the photosensitive coloring agent, and the content of the sensitizer (E) is 5-40 wt.% based on 100 wt.% of the photopolymerization initiator (D).

Description

  The present invention relates to a photosensitive coloring composition, and in particular, a photosensitive coloring composition used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, etc., particularly a thin film transistor (TFT) type color. A photosensitive coloring composition for use in a color filter of a color filter on array system (hereinafter sometimes abbreviated as COA system), comprising a filter segment having a colored layer formed on a driving substrate of a liquid crystal display device, and The present invention relates to a color filter formed using a photosensitive coloring composition.

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display. By providing a color filter between these two polarizing plates, color display is possible, and in recent years it has come to be used in televisions, personal computer monitors, etc., so there is a demand for higher brightness and higher contrast for color filters. Is growing.

  The color filter is formed by forming a colored layer directly or through a passivation film such as a silicon nitride film on a transparent substrate such as glass or a driving substrate on which a thin film transistor (TFT) is disposed. It consists of fine band (striped) filter segments of different colors or more arranged in parallel or intersecting, or fine filter segments arranged in a fixed arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  The liquid crystal used in such a liquid crystal display device is easily affected by the electrical characteristics of members such as a color filter inherent in the liquid crystal display device, and adversely affects liquid crystal orientation disorder and switching performance due to liquid crystal contamination. Display defects may become a problem. In order to solve such a problem, the color layer of the color filter is required to have insulation, and it is necessary to increase the insulation by increasing the film thickness or to form a color film having a low dielectric constant. In order to solve such a problem, a method of selecting a dielectric loss tangent of two layers obtained by laminating an overcoat layer in a color layer of a green (green) pixel within a specific range has been studied (see Patent Document 1). .

  In particular, a colored layer is formed directly or via a passivation film such as a silicon nitride film on a driving substrate on which a thin film transistor (TFT), which has recently been attracting attention, and a substrate on which the colored layer is formed. In the COA method (see Patent Document 2) in which a transparent electrode for driving a liquid crystal is bonded to a substrate formed by vapor deposition or sputtering (see Patent Document 2), coloring is directly performed on a driving substrate on which a thin film transistor (TFT) is arranged. In order to form a layer, the pixel aperture ratio (aperture ratio) can be greatly increased, so that it is possible to achieve high brightness and low power consumption. There is a problem that it is easily affected by characteristics.

  In order to solve such a problem, the color filter segment is usually formed with a thickness of about 1.6 to 2 μm, whereas in the COA system, the color filter is electrically formed with a thickness of about 3 μm. In many cases, this is handled by a method that reduces the influence of characteristics. Furthermore, it is necessary to provide a contact hole for connecting the transparent electrode and the thin film transistor (TFT) in the color filter segment because the thick color filter segment is formed on the thin film transistor (TFT) instead of the insulating layer. For this reason, the photosensitive coloring composition forming the pixel needs to have a resolution superior to that of a normal photosensitive coloring composition. The resolution of the photosensitive coloring composition is generally adjusted by the type and amount of the photopolymerization initiator and monomer, and the photopolymerization initiator and monomer with low sensitivity are selected or the amount is selected. In some cases, it can be improved by reducing the thickness, but on the other hand, the adhesiveness between the photosensitive coloring composition and the glass substrate is lowered due to a decrease in sensitivity, and pattern peeling is likely to occur.

JP 2004-117537 A JP 2004-94263 A

  An object of the present invention is to provide a photosensitive coloring composition having no adhesion even in a thick film, having a high resolution, and having excellent adhesion without causing pattern peeling, and a color filter suitable for a COA system using the same. The purpose is to do.

[一般式（１）において、Ｒ¹、Ｒ²は−Ｈ、−ＣＨ₃、−Ｃ₂Ｈ₅のいずれかであり、Ｒ³は−ＣＨ₃、−ＯＣＨ₃、−ＯＣ₂Ｈ₅のいずれかを表す。] The subject is at least one compound selected from the group consisting of a colorant (A), a resin (B), a photopolymerizable monomer (C), an acetophenone compound, an acylphosphine oxide compound, and an oxime compound. A photosensitive coloring composition comprising a photopolymerization initiator (D) containing a sensitizer (E) containing a compound having a structure represented by the following general formula (1), the photopolymerization initiator: The content of (D) is 3 to 20% by weight in the total 100% by weight of the solid content of the photosensitive coloring composition, and the content of the sensitizer (E) is the photopolymerization initiator (D). This is solved by the photosensitive coloring composition, which is 5 to 40 parts by weight with respect to 100 parts by weight.
General formula (1)

[In General Formula (1), R ¹ and R ² are any of —H, —CH ₃ , and —C ₂ H ₅ , and R ³ is any of —CH ₃ , —OCH ₃ , and —OC ₂ H ₅ . Represents ]

  In the present invention, the colorant (A) is C.I. I. The photosensitive coloring composition is a green pigment containing CI Pigment Green 58.

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

  The present invention also relates to the color filter, wherein the substrate is a driving substrate for a thin film transistor (TFT) type color liquid crystal display device.

The photosensitive coloring composition of the present invention comprises a group consisting of a colorant (A), a resin (B), a photopolymerizable monomer (C), an acetophenone compound, an acylphosphine oxide compound, and an oxime compound. A photosensitive coloring composition comprising a photopolymerization initiator (D) containing at least one selected compound and a sensitizer (E) containing a compound having a structure represented by the following general formula (1): The content of the photopolymerization initiator is 3 to 20% by weight based on the solid content of the photosensitive coloring composition, and the content of the sensitizer (E) is that of the photopolymerization initiator (D). By setting the amount to 5 to 40% by weight based on the total weight, no foreign matter is generated even in the thick film, the resolution is high, and the adhesion to a base material such as a glass substrate is also good.
Therefore, by forming a filter segment using the photosensitive coloring composition of the present invention, it is possible to provide a color filter having high resolution without generation of foreign matter even in a thick film, and therefore, for the COA method. The color filter is also suitable, and a liquid crystal display device with high resolution and low power consumption can be manufactured by using the color filter.

First, the photosensitive coloring composition of this invention is demonstrated.
The photosensitive coloring composition of the present invention comprises a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and a sensitizer (E). , Containing.

<Colorant (A)>
Examples of the colorant used in 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, 166, 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, Red pigments such as 280, 281, 282, 283, 284, 285, 286, or 287 are used. Further, basic dyes exhibiting red color, acidic dyes, and salt-forming compounds of these dyes can also be 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, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or may be used in combination of a yellow pigment 221, and the like. Further, basic dyes exhibiting orange and / or yellow, acid dyes, and salt-forming compounds of these dyes can also be used.

  Examples of the colorant used in the green coloring composition include C.I. I. Pigment green 7, 10, 36, 37, 58 and the like.

  Among them, C.I. I. It is preferable to use Pigment Green 58 in that high brightness can be achieved. C. I. Pigment Green 58 is difficult to ensure dispersion stability compared to other pigment types due to its high acidity, but by using the photosensitive coloring composition of the present invention, the crystalline foreign matter of the coating film is also reduced. It is possible to suppress.

  A yellow pigment can be used in combination with the green coloring composition. Examples of yellow pigments that can be used in combination include 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, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, basic dyes exhibiting yellow, acidic dyes and salt-forming compounds of these dyes can be used in combination.

  For example, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, or 64 can be used as the colorant used in the blue coloring composition. . A purple pigment such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, or 50 can be used in combination with the blue coloring composition. Further, basic dyes exhibiting purple, acidic dyes and salt-forming compounds of these dyes can be used in combination.

(Miniaturization of pigment)
The pigment used in the present invention can be refined by a salt milling treatment. The primary particle diameter of the pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with a high contrast ratio, it is preferably 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, with respect to 100 or more pigment particles, the volume of each particle is obtained by approximating it with 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 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, 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 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  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 the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Resin (B)>
The resin disperses the colorant, and examples thereof include a thermoplastic resin and a thermosetting resin.
The resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  The weight average molecular weight (Mw) of the 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 (A) 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.

  Further, from the viewpoint of pigment dispersibility, developability, and heat resistance, a carboxyl group that functions as a pigment adsorbing group and an alkali-soluble group during development, an aliphatic group and an aromatic group that function as an affinity group for a pigment carrier and a solvent. The balance is important for pigment dispersibility, developability, and durability, 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 resin is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the colorant because the film formability and various resistances are good, and since the colorant concentration is high and good color characteristics can be expressed. It is preferably used in an amount of 500 parts by weight or less.

(Thermoplastic resin)
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and 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 energy ray curable resin having an ethylenically unsaturated active double bond include a resin into which an unsaturated ethylenic double bond is introduced by the following methods (a) and (b).

<Method (a)>
As the method (a), 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 an unsaturated monobasic acid having an unsaturated elenic double bond is added, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to give an unsaturated ethylenic double bond and a carboxyl group. 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 similar method to the method (a), 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 (b)>
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or by copolymerizing with another monomer. 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 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 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 unsaturated ethylenic 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 resin)
Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

<Photopolymerizable monomer (C)>
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 (C) is preferably 10 to 50% by weight in a total of 100% by weight of the solid content of the coloring composition, and 20 to 20% from the viewpoint of photocurability and developability. More preferably, it is 40% by weight.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 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 diglycy Luether di (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 include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator (D)>
The colored composition for a color filter of the present invention is prepared in the form of an alkali developing type colored resist material by adding a photopolymerization initiator to cure the composition by ultraviolet irradiation and form a filter segment by a photolithographic method. .
The photopolymerization initiator (D) of the present invention includes at least one compound selected from the group consisting of acetophenone compounds, acylphosphine oxide compounds, and oxime compounds.

The compounding quantity of a photoinitiator (D) is 3-20 weight% in the total of 100 weight% of solid content of the photosensitive coloring composition. If it is less than 3% by weight, the adhesion to the substrate is poor, and if it exceeds 20% by weight, there is a problem in resolution.
More preferably, the lower limit is 5% by weight and the upper limit is 18% by weight.

As at least one compound selected from the group consisting of acetophenone compounds, acylphosphine oxide compounds, and oxime compounds,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane- Acetophenone compounds such as 1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone,
Acylphosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide;
1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 ′ And oxime compounds such as -methoxy-naphthyl) ethylidene) hydroxylamine.

  More preferred are acetophenone compounds and acyl phosphine oxide compounds, and the most preferred examples include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, which has an internal curability. Because of the excellent initiator, the cross-sectional shape tends to become a forward taper after the film is cured, and the shape is excellent.

Further, as a photopolymerization initiator that can be used in combination, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal and other benzoin compounds, benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, Benzophenone compounds such as hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone Thioxanthone compounds such as 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, , 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- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-tri Triazine compounds such as gin, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (o-methoxy) Phenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-methylphenyl) biimidazole, Imidazole compounds such as 9,10-phenanthrenequinone, quinone compounds such as camphorquinone and ethylanthraquinone, borate compounds, carbazole compounds, titanocene compounds and the like.
These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

[一般式（１）において、Ｒ¹、Ｒ²は−Ｈ、−ＣＨ₃、−Ｃ₂Ｈ₅のいずれかであり、Ｒ³は−ＣＨ₃、−ＯＣＨ₃、−ＯＣ₂Ｈ₅のいずれかを表す。] <Sensitizer (E)>
The sensitizer (E) in the present invention contains a compound having a structure represented by the following general formula (1), and the content of the sensitizer (E) is 100 parts by weight of the photopolymerization initiator (D). It is characterized by being 5 to 40 parts by weight.
When the amount is less than 5 parts by weight, the adhesion to the substrate is poor, and when it exceeds 40 parts by weight, the resolution becomes a problem.
More preferably, the lower limit is 12 parts by weight and the upper limit is 36 parts by weight.
General formula (1)

[In General Formula (1), R ¹ and R ² are any of —H, —CH ₃ , and —C ₂ H ₅ , and R ³ is any of —CH ₃ , —OCH ₃ , and —OC ₂ H ₅ . Represents ]

  Preferred compounds represented by the above general formula (1) include 4-dimethylaminoacetophenone, 4-diethylaminoacetophenone, methyl 4- (N, N-dimethylamino) benzoate, and most preferably 4 -Dimethylaminoacetophenone. These compounds are C.I. I. Also in the photosensitive resin composition using the green pigment containing the pigment green 58, generation | occurrence | production of a foreign material can be suppressed and it is preferable.

  Sensitizers that can be used in combination include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by 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, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrins Derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, Examples include spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler ketone derivatives, and the like.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Among the sensitizers, specific examples of sensitizers that can be used in combination include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole and the like can be mentioned.
Two or more kinds of sensitizers may be used in any ratio as required.

<Solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and applied to a glass substrate or the like so as to have a dry film thickness of 0.5 to 5.0 μm. A solvent can be included to facilitate the formation of the segments.
Examples of the solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 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-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate , 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, ethylene glycol monohexyl ether, ethylene glycol Methyl 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 glycol 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, methylcyclohexanol, n-amyl acetate, n-butyl acetate, Acetate Amyl, isobutyl acetate, propyl acetate, and a dibasic acid ester and the like.

Among them, from the viewpoint of storage stability of the colored composition of the present invention, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol acetates such as ethylene glycol monoethyl ether acetate, benzyl alcohol, etc. It is preferable to use ketones such as aromatic alcohols and cyclohexanone.
A solvent can be used individually by 1 type or in mixture of 2 or more types. Further, the solvent is preferably used in an amount of 800 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the color composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. .

<Production of photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be prepared as a solvent developing type or alkali developing type photosensitive coloring composition. The solvent development type or alkali development type photosensitive coloring composition is generally a thermoplastic resin, a thermosetting resin or a photosensitive resin, a photopolymerizable monomer, a photopolymerization initiator, A pigment is dispersed in a composition containing a solvent.

The photosensitive coloring composition of the present invention comprises a three-roll mill, a two-roll mill by mixing a colorant (A), a resin (B), and, if necessary, a dispersion aid, a solvent, and an additive. The pigment dispersion is prepared by dispersing the pigment in the resin solution by dispersing with a kneader, horizontal sand mill, vertical sand mill, annular bead mill, or attritor, and then photopolymerization is performed. It is possible to adjust by mixing a photopolymerizable monomer (C), a photopolymerization initiator (D), a sensitizer (E), and, if necessary, a solvent, other dispersion aids, and additives. it can.
The photopolymerization initiator (D) and the sensitizer (E) may be added at the stage of preparing the photosensitive coloring composition, or may be added later to the prepared photosensitive coloring composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the pigment carrier using the dispersion aid is used. If so, a color filter with high spectral transmittance can be obtained.

Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.
In the present invention, a pigment derivative is particularly preferable, and the structure thereof is a compound represented by the following general formula (2).
P-Ln Formula (2)
(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group n: an integer of 1 to 4 is there)
Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. What is currently used can be used, These can be used individually or in mixture of 2 or more types.
The blending amount of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, and most preferably 35 parts by weight or less with respect to 100 parts by weight of the colorant.

  The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 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, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored 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. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in a total of 100% by weight of the coloring composition.

  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 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. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. 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. A storage stabilizer can be used in the quantity of 0.1-10 weight part with respect to 100 weight part of coloring agents contained in a coloring composition.

  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 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the colorant contained in the coloring composition.

<Removal of coarse particles>
The coloring 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 using the photosensitive coloring composition of this invention and the manufacturing method of a color filter are demonstrated.

  The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. The said filter segment is formed on a base material by apply | coating the photosensitive coloring composition of this invention by a spin coat system or a die coat system.

  As the base material of the color filter, glass plates such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, etc. with high transmittance for visible light, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. A transparent substrate such as a resin plate or a reflective substrate can be used. These substrates may be subjected to appropriate pretreatments such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after forming the panel.

  If a black matrix is formed in advance before forming the filter segments on these transparent or reflective substrates, 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. Alternatively, a thin film transistor (TFT) formed in advance on the transparent substrate or the reflective substrate may be used as a driving substrate for a thin film transistor (TFT) type color liquid crystal display device, 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.

  Here, a method for forming a colored layer on the TFT substrate will be described. First, on the surface of the TFT substrate or on the surface of the substrate on which a passivation film such as a silicon nitride film is formed on the surface of the driving substrate, a light shielding layer is formed so as to divide the pixel forming portion as necessary. After forming and applying a colored composition in which a pigment is dispersed on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, this coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked, whereby the pixel pattern has a predetermined arrangement. An arranged pixel array is formed. The photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel.

  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. An antifoaming agent or a surfactant can also be added to the developer.

  As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. After forming, UV exposure can also be performed.

The dry thickness of the coating thickness when forming the filter segment on the transparent substrate or the reflective substrate is preferably 0.1 to 5.0 μm, more preferably 0.5 to 3.0 μm.
In particular, when the colored composition of the present invention is used in a COA system, insulation is required to prevent crosstalk occurring between the gate electrode and the transparent electrode, and a thick film is preferable. The film thickness is preferably 0.1 to 10 μm, more preferably 0.5 to 5.0 μm.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
Moreover, the polymerization average molecular weight (Mw) of the acrylic resin was measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw) in terms of polystyrene.

First, a method for producing an acrylic resin solution, a method for preparing a resin-type dispersant solution, and a method for producing a pigment dispersion used in Examples and Comparative Examples will be described.
<Method for producing acrylic resin solution>
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare an acrylic resin solution.

<Preparation Method of Resin Type Dispersant Solution>
A commercially available resin type dispersant, “EFKA4300” manufactured by Ciba Japan Co., Ltd., and ethylene glycol monomethyl ether acetate were used to prepare a solution having a nonvolatile content of 40% by weight and used as a resin type dispersant solution.

<Method for producing pigment dispersion>
(Production of green pigment dispersion)
8.0 parts of zinc halide phthalocyanine green pigment (CI Pigment Green 58), 3.0 parts of nickel azo complex pigment (CI Pigment Yellow 150) (“E4GN” manufactured by LANXESS), 2 A mixture of 40.0 parts of the acrylic resin solution and 46.5 parts of the above-mentioned acrylic resin solution and 46.5 parts of ethylene glycol monomethyl ether acetate was stirred and mixed uniformly. Manufactured by “Mini Model M-250 MKII”) for 5 hours and then filtered through a 5.0 μm filter to prepare a green pigment dispersion.

(Preparation of red pigment dispersion)
Diketopyrrolopyrrole pigment (CI Pigment Red 254) ("Irga Four Red BF" manufactured by Ciba Japan) 8.0 parts, nickel azo complex pigment (CI Pigment Yellow 150) ("E4GN" manufactured by LANXESS) A mixture of 3.0 parts, 2.5 parts of the resin-type dispersant solution, 40.0 parts of the acrylic resin solution, and 46.5 parts of ethylene glycol monomethyl ether acetate was uniformly stirred and mixed. Using a zirconia bead, the mixture was dispersed in an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours, and then filtered through a 5.0 μm filter to prepare a red pigment dispersion.

(Preparation of blue pigment dispersion)
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) (BASF “Heliogen Blue L-6700F”) 11.0 parts, resin-type dispersant solution 2.5 parts, acrylic resin solution 40.0 parts , And 46.5 parts of ethylene glycol monomethyl ether acetate were uniformly stirred and mixed, and then 5 hours with Eiger Mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. After dispersion, the mixture was filtered through a 5.0 μm filter to prepare a blue pigment dispersion.

[Examples 1 to 14 and Comparative Examples 1 to 11]
<Preparation of coloring composition>
The mixture having the composition described in Tables 1 to 3 was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain green, red, and blue colored compositions, respectively.

Abbreviations in Tables 1 to 3 are shown below.
Initiator 1: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“IRGACURE 819” manufactured by BASF)
Initiator 2: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“IRGACURE 379” manufactured by BASF)
Initiator 3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("IRGACURE 907" manufactured by BASF)
Initiator 4: 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]
("IRGACURE OXE 01" manufactured by BASF)
Initiator 5: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (“Biimidazole” manufactured by Kurokin Kasei)

Sensitizer 1: 4-dimethylaminoacetophenone ("DMA" manufactured by Daiki Fine)
Sensitizer 2: 2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Sensitizer 3: 4,4'-bis (diethylamino) benzophenone ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)

Monomer: KAYARAD DPCA-60
(Nippon Kayaku Co., Ltd.)
Solvent 1: Propylene glycol monomethyl ether acetate Solvent 2: Ethyl 3-ethoxypropionate

<Adhesion, resolution, cross-sectional shape>
Using the spin coater, the color filter coloring compositions obtained in the examples and comparative examples were formed on a substrate in which a silicon nitride film was formed on the surface of a TFT liquid crystal driving substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm. The film was coated at a rotational speed such that the film thickness after drying was 3.0 μm, dried under reduced pressure, and then exposed to ultraviolet light using an ultrahigh pressure mercury lamp through a photomask with an integrated light amount of 50 mJ and an illuminance of 20 mW. Thereafter, a 0.2 wt% sodium carbonate aqueous solution was used as a developer, and the uncured portion of the coating film was removed to form a pattern including a regular octagonal through hole having a diameter of 30 μm and a thin line having a thickness of 50 μm. Thereafter, post-baking was performed at 230 ° C. for red: 60 minutes, green: 40 minutes, blue: 20 minutes, and an evaluation substrate was prepared.
Using the prepared substrate, adhesion, resolution, and cross-sectional shape were evaluated according to the following criteria.
Moreover, about the thing with bad adhesiveness, resolution and cross-sectional shape evaluation were not performed.
The results are shown in Table 2.

(Adhesion)
Visual evaluation was performed in three stages according to the following criteria.
○: No pattern peeling is observed Δ: Pattern peeling is slightly recognized ×: Pattern peeling is recognized

(Resolution)
The hole diameter was measured with analysis software (Image-Pro, manufactured by Planetron Co., Ltd.) using an optical microscope, and evaluated according to the following criteria.
○: A hole of 25 μm or more can be formed with respect to a mask hole diameter of 30 μm. Δ: A hole of 15 μm or more to less than 25 μm can be formed with respect to a mask hole diameter of 30 μm.

(Cross-sectional shape)
The fine line portion of the pattern was evaluated in three stages using a scanning electron microscope (SEM) according to the following criteria.
○: Forward tapered shape (the area of the surface in contact with the substrate is larger than the area of the surface far from the substrate)
Δ: non-tapered shape (section is almost rectangular)
×: Inverted taper shape (the area of the surface in contact with the substrate is smaller than the area of the surface far from the substrate)

<Coating foreign material test method>
The colored composition for color filter obtained in Examples and Comparative Examples was applied on a glass substrate having a size of 100 mm × 100 mm and a thickness of 0.7 mm so that the dry coating film was about 3.0 μm, and was heated at 230 ° C. in an oven at 20 ° C. A test substrate heated for a minute was prepared and the number of particles was counted. The evaluation was performed by observing the surface using a metal microscope “BX60” manufactured by Olympus System. The magnification was 500 times, and the number of particles that were observable in arbitrary 5 fields of view through transmission was counted. In the following evaluation results, ◯ is good, Δ is a level at which no foreign matter is present, but there is no problem in use, and x is uneven coating due to foreign matter.
○: Less than 5 Δ: 5 or more, less than 50 ×: 50 or more Evaluation results are shown in Table 4.

Each of the photosensitive coloring compositions obtained in Examples 1 to 14 has a good cross-sectional shape even in a thick film such as a dry film thickness of 3 μm, compared to the comparative example, and does not cause pattern peeling and is excellent in adhesion. It was.
Thus, it is apparent that the photosensitive coloring composition for forming a color filter used in the COA method is excellent.

  Further, when Examples 2, 6, 7 and 8 differing only in the type of photopolymerization initiator are compared, in Examples 2, 6, and 7 where the photopolymerization initiator is an acetophenone compound or an acylphosphine oxide compound. Example 2 in which the cross-sectional shape was excellent and the photopolymerization initiator was an acyl phosphine oxide-based compound was a result of further excellent adhesion and resolution.

  Further, in Examples 1 to 8, C.I. I. Even if Pigment Green 58 was included, an excellent effect that no foreign matter was generated was confirmed.

  In addition, even when a dry film thickness of 2 μm used for a normal color filter is evaluated using the same method for resolution and pattern shape, excellent glass adhesion and pattern similar to those for a thick film are also obtained. Shape and high resolution.

Claims (4)

Photopolymerization comprising at least one compound selected from the group consisting of a colorant (A), a resin (B), a photopolymerizable monomer (C), an acetophenone compound, an acylphosphine oxide compound, and an oxime compound. A photosensitive coloring composition comprising an initiator (D) and a sensitizer (E) containing a compound having a structure represented by the following general formula (1), wherein the photopolymerization initiator (D) The content is 3 to 20% by weight in a total of 100% by weight of the solid content of the photosensitive coloring composition, and the content of the sensitizer (E) is 100 parts by weight of the photopolymerization initiator (D). The photosensitive coloring composition characterized by being 5-40 weight part with respect to it.
General formula (1)

[In General Formula (1), R ¹ and R ² are any of —H, —CH ₃ , and —C ₂ H ₅ , and R ³ is any of —CH ₃ , —OCH ₃ , and —OC ₂ H ₅ . Represents ]   The colorant (A) is C.I. I. The photosensitive coloring composition according to claim 1, wherein the photosensitive coloring composition is a green pigment containing CI Pigment Green 58.   A color filter comprising a filter segment formed using the photosensitive coloring composition according to claim 1 on a substrate.   4. The color filter according to claim 3, wherein the base material is a driving substrate for a thin film transistor (TFT) type color liquid crystal display device.