KR20070070072A - Photo-curable coloring composition, color filter, and liquid crystal display device - Google Patents

Abstract

Provided is a photocurable coloring composition, which contains a high concentration of a coloring agent, is useful for producing a color filter, particularly a black matrix, and shows excellent developing properties and high color purity. The photocurable coloring composition comprises a coloring agent, an alkali soluble resin, a polymerizable compound and a photopolymerization initiator, wherein the alkali soluble resin has at least one group selected from the group consisting of alkali soluble groups, polymerizable double bonds and hydrophobic groups represented by the following formulae(a) and (b) in a side chain thereof. The photocurable coloring composition comprises the coloring agent in an amount of at least 30 wt% based on the total weight of the non-volatile components.

Description

Photo-curable coloring composition, color filter, and liquid crystal display device {PHOTO-CURABLE COLORING COMPOSITION, COLOR FILTER, AND LIQUID CRYSTAL DISPLAY DEVICE}

1 is a graph showing the linewidth sensitivity of Examples 1 and 2 and Comparative Examples 1 and 2. FIG.

2 is a graph showing the linewidth sensitivity of Examples 3 and 6 and Comparative Examples 3 and 6. FIG.

3 is a graph showing line width sensitivity of Example 4 and Comparative Example 4. FIG.

4 is a graph showing the linewidth sensitivity of Example 5 and Comparative Example 5. FIG.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to photocurable coloring compositions and color filters, and in particular, to photocurable coloring compositions having high colorant concentrations and color filters, in particular, to photocurable coloring compositions and liquid crystal displays using the same. will be.

In general, liquid crystal displays have red (R), green (G), blue (B), and black (BM) (hereinafter, simply referred to as "R", "G", "B", and "BM"). Two substrates including a color filter substrate having a colored image formed thereon, a liquid crystal material disposed between the two substrates, and a pair of electrodes disposed on each substrate facing each other to form a pair. . The black image serves to cut off stray light from adjacent pixels to enhance visibility of the colored pixels, or to hide electrodes, and is generally formed to isolate colored pixels such as RGB. For example, it can arrange | position so that pixel of RGB color may be divided | segmented into matrix form, and is called black matrix.

The colored image constituting the color filter is generally formed by a photoresist method. Specifically, for example, a coating liquid of a coloring composition obtained by uniformly dispersing or dissolving a colorant such as an organic pigment, dye, or carbon black in a photocurable resin component After apply | coating on substrates, such as glass, and drying and prebaking as needed, it can expose in a desired pattern, and can develop and form. In addition, in order to harden | cure further, heat processing (post-baking) is performed as needed.

In recent years, higher optical density is required for black matrices formed between colored pixels of chromatic color, such as RGB of a color filter. That is, in recent years, the spread of thin-screen televisions and the like is remarkable, and the color filter is particularly widespread for TV applications such as liquid crystal televisions. In liquid crystal televisions and the like, the illuminance of the backlight is higher than in the conventional monitor applications, and in addition, better image quality is required in terms of color reproducibility, display contrast, and the like, and the demand for a high optical density black matrix is increasing.

In order to make the optical density of a black matrix high, it is necessary to raise the content concentration of the black agent (carbon black etc.) in the curable composition for black matrix formation.

In addition, colored parts such as RGB are also required to form pixels with high color purity due to high color reproducibility. For this reason, high content concentration of a coloring agent is calculated | required and high dispersion stability is required. In addition, high contrast performance without color loss is required, and it is necessary to make colorants such as pigments into fine particles. However, when the particle size is reduced, the surface area of the colorant is increased, and thus it has become important to secure higher dispersion stability.

Conventionally, the vinyl ester resin which can be used as a photosensitive resin material suitable for colored pixels, such as a black matrix and RGB, is disclosed (for example, refer patent documents 1-2), and alkali developability, heat resistance after hardening, solvent resistance, etc. are improved. It is said to be possible.

(Patent Document 1) Japanese Patent No. 3659639

(Patent Document 2) Japanese Patent Application Laid-Open No. 2001-89533

However, in order to obtain a high optical density and high color purity, for example, when the concentration of the black agent and the pigment is increased, the light transmittance decreases when the coating film made of the curable composition is exposed. There is a problem that it is easy to cause a decrease in development margin and development latitude.

For this reason, even at high color purity with high pigment concentration, the pattern shape does not become undercut in the production of color filters (such as for TVs), so that the taper angle can be arbitrarily prepared, and there is a wide development latitude, and furthermore, during production time The realization of the color filter material by which the sensitivity in the required exposure process is acquired was anticipated and desired.

The present invention has been made in view of the problems of the prior art, and the photocurable coloring composition, optical, which maintains high sensitivity and has good developability of developing margin and developing latitude even when a component composition having a high content ratio of the colorant is used An object of the present invention is to provide a colored pixel having high color purity with a high density and sharp black matrix and high contrast, and to provide a high quality color filter and a liquid crystal display device using the same.

In addition, "developing margin" refers to the change in the line width of the pattern and the stability of the pattern shape with respect to the developing time. The developing latitude is the time from the expression of the pattern to the pattern peeling (that is, the line width and the pattern shape can be maintained. Length of development time).

 In the present invention, an alkali-soluble resin used in the case of a component composition having a high content of a colorant is introduced into the alkali-soluble resin as a polymerizable double bond and a hydrophobic group by introducing a glycidyl group or the like into the side chain. The knowledge that the acryl-type polymer was useful is acquired, and it was achieved based on this knowledge.

Specific means for achieving the above object is as follows.

<1> Photocurable coloring composition containing a coloring agent, alkali-soluble resin, a polymeric compound, and a photoinitiator WHEREIN: The said alkali-soluble resin has an alkali-soluble group, a polymeric double bond, and the following hydrophobic groups (a) and ( It is an acrylic copolymer which has at least one of b), The photocurable coloring composition characterized by the above-mentioned.

<2> Content of the said coloring agent is a photocurable coloring composition as described in said <1> which is 30 mass% or more of the total mass of a nonvolatile component.

<3> The said coloring agent is black, and content of the said coloring agent is the photocurable coloring composition as described in said <1> or <2> which is 47 mass% or more of the total mass of a nonvolatile component.

<4> The said black coloring agent is the photocurable coloring composition as described in said <3> which is at least 1 sort (s) chosen from carbon black, titanium black, and graphite.

<5> The said coloring agent is red, and content of the said coloring agent is the photocurable coloring composition as described in said <1> or <2> which is 30 mass% or more of the total mass of a nonvolatile component.

<6> The said coloring agent is green, and content of the said coloring agent is the photocurable coloring composition as described in said <1> or <2> which is 45 mass% or more of the total mass of a nonvolatile component.

<7> The said coloring agent is blue, and content of the said coloring agent is the photocurable coloring composition as described in said <1> or <2> which is 30 mass% or more of the total mass of a nonvolatile component.

<8> It is a color filter formed using the photocurable coloring composition in any one of said <1>-<7>.

<9> It is a liquid crystal display device which has the color filter as described in said <8>.

Hereinafter, the photocurable coloring composition of this invention, the black matrix using this and the colored pixel of high color purity are demonstrated in detail.

<Photocurable coloring composition>

The photocurable coloring composition of this invention contains a coloring agent, alkali-soluble resin, a polymeric compound, and a photoinitiator at least, and can be comprised using another component as needed.

Alkali-soluble resin

The photocurable coloring composition of the present invention is at least one kind of acrylic copolymer having an alkali-soluble group, a polymerizable double bond and at least one of the following hydrophobic groups (a) and (b) in the side chain as an alkali-soluble resin. May be referred to as an "acrylic copolymer according to the invention".

Since this acrylic copolymer is contained, when a coloring agent is contained in high concentration (preferably 30 mass% or more of the nonvolatile content in a composition), pattern exposure is performed with high sensitivity, and the developer at the time of image development permeates into the film | membrane. It is also effective in shortening the tack time of the process because it has excellent controllability to optimize the development speed by controlling.

The acrylic copolymer according to the present invention has an alkali-soluble group in its side chain, and examples of the alkali-soluble group include a carboxyl group, a phosphoric acid group, a sulfonic acid group and the like, and among these, a carboxyl group is preferable. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, partially esterified maleic acid, and the like, and acrylic acid and methacrylic acid are particularly preferred.

Moreover, since an alkali-soluble group has in a side chain, favorable developability can be ensured.

The acrylic copolymer according to the present invention has a polymerizable double bond in the side chain thereof, and examples of the polymerizable double bond include acryloyl group, methacryloyl group, allyl group, and the like. Among them, acryloyl group and meta Cryloyl groups are preferred. Since a polymerizable double bond is based on a side chain, when the content density | concentration of a coloring agent increases, sensitivity can be kept high and it also contributes to shortening a tack time.

The acrylic copolymer according to the present invention has at least one of the following hydrophobic groups (a) and (b) in the side chain thereof, and has these hydrophobic groups in the side chain, thereby controlling the penetration of the developer into the film during development to increase the development speed. It can be adjusted appropriately. In addition, there is no chemical coloring over time, and even when color pigments such as red, green, and blue are used as colorants, deterioration of color characteristics with time can be reduced.

The acrylic copolymer according to the present invention can be synthesized by at least one copolymerization of at least one monomer of an acrylic monomer and another monomer other than the acrylic monomer. Alkali-soluble groups, polymerizable double bonds, and hydrophobic groups of the side chains may be present in any of the acrylic monomers and the other monomers, or may be present in both of them. In addition, at least one copolymer of at least one acrylic monomer and at least one copolymer of other monomers other than the acrylic monomer is synthesized by a conventional method, and then further reacted to this to introduce alkali-soluble groups, polymerizable double bonds, and hydrophobic groups into the side chain. It can also synthesize | combine by making it.

As said acryl-type monomer, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl acrylate, cyclohexyl acrylate styrene, α-methylstyrene And vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like.

Moreover, styrene etc. are mentioned as a monomer other than the above, for example.

As for the weight average molecular weight of the acrylic copolymer which concerns on this invention, 5,000-30,000 are preferable, More preferably, it is 7,000-20,000.

In addition, in the acrylic copolymer according to the present invention, the proportion of the alkali-soluble group is preferably 10 to 60, more preferably 15 to 50, and particularly preferably 20 to 40, in a molar ratio with respect to 1 molecule of the acrylic copolymer. The ratio of the polymerizable double bond is preferably 10 to 60, more preferably 15 to 50, particularly preferably 20 to 40, and the ratio of the hydrophobic group to the acrylic copolymer per molecule of the acrylic copolymer. 5-70 are preferable at molar ratio with respect to 1 molecule of copolymerization, More preferably, it is 10-60, Especially preferably, it is 20-40.

In addition, presence of alkali-soluble group, a polymerizable double bond, and a hydrophobic group in a side chain can be confirmed by acid value measurement, IR (infrared absorption spectrum) analysis, MS (mass spectrometry), for example.

The specific example of the acrylic copolymer which concerns on this invention is demonstrated. The structures of the hydrophobic groups (a) and (b) are tricyclo [5.2.1.0 ^2.6 ] decane skeletons, but this skeleton is also called dicyclopentane skeleton. In the present invention, the notation of a dicyclopentane skeleton is used. The acrylic copolymer according to the present invention is dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentanyloxy acrylate, dicyclopentenyloxy acrylate, dicyclopentanyloxyethyl acrylate, dicyclopentenyloxyethyl It is a compound which copolymerized the acrylate and the compound which modified these acrylates with methacrylate etc. with the other copolymerizable acrylic monomer.

It is essential to contain an alkali-soluble monomer with the above-mentioned copolymerizable acrylic monomer. As an alkali-soluble monomer, it is (meth) acrylic acid, maleic acid, maleic anhydride, crotonic acid, itaconic acid, etc., and it is preferable that it is a composition which made the acid value of an acrylic resin become the range of 30-200 mgKOH / g. If an acid value is in the said range, a pigment will be disperse | distributed favorably.

Moreover, it is preferable to copolymerize an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. These copolymerization components have high lipophilic properties, which enhance the solubility in a solvent and make the resist liquid uniform.

Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and isobutyl ( Meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl ( Meth) acrylate, cyclohexyl (meth) acrylate, etc. can be mentioned. In addition, the vinyl compound may include styrene, α-methylstyrene, vinyltoluene, glycidyl (meth) acrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl (meth) acrylate, Polystyrene macromonomers, polymethylmethacrylate macromonomers, and the like. Particularly preferred as these lipophilic monomers are phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. Monomers other than these copolymerizable can be used individually by 1 type or in combination of 2 or more types.

Moreover, the compound which has a hydroxyl group and a polyalkylene oxide group can also be copolymerized as needed. These groups have high hydrophilicity, and are effective in adjusting the developing speed in alkali development by containing in the resin. Specific examples include hydroxyalkyl acrylate and hydroxyaryl acrylate as hydroxy group-containing (meth) acrylates. The alkyl group of the hydroxyalkyl acrylate preferably has 2 to 12 carbon atoms. In addition, the alkyl group may be any of linear, branched and cyclic. Examples of the substituent include an aryl group, a halogen group, a phenyl group and an alkoxy group. Specific examples of the alkyl group include ethyl group, propyl group, butyl group, hexyl group, octyl group, cyclohexyl group, benzyl group and the like. Particularly preferred hydroxy group-containing (meth) acrylates are hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.

Moreover, it is preferable that the aryl group of hydroxyaryl acrylate has 6-12 carbon atoms. Moreover, the hydrogen atom may be substituted by the substituent in the aryl group. As said substituent, an alkyl group, an aryl group, a halogen group, a phenyl group, an alkoxy group etc. can be mentioned. Specific examples of the aryl group include phenyl group, tolyl group, naphthyl group, benzyl group and the like. The said hydroxyl group containing (meth) acrylate can be used individually by 1 type or in combination of 2 or more types.

Examples of the compound having a polyalkylene oxide group include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol polypropylene glycol mono (meth) acrylate, or these terminal OH groups in which an alkyl group is sealed. Compound is preferred. About 3-20 are preferable and, as for the repeating unit of a polyalkylene group, 5-10 are more preferable.

The method of providing an unsaturated bond to resin has the following method, and can be used suitably.

(1) urethane-modified polymerizable double bond-containing acrylic resin obtained by reaction of an acrylic resin containing a carboxyl group or an OH group, an isocyanate group and a (meth) acryloyl group

(2) Unsaturated-group containing acrylic resin obtained by reaction of the acrylic resin containing a carboxyl group, and the compound which has an epoxy group and a polymerizable double bond together in a molecule | numerator.

(3) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond.

Among the above, the resin synthesis method of (1) and (2) is especially preferable.

Specifically, the COOH group and the OH group of the quaternary copolymers of dicyclopentanyl methacrylate, methacrylic acid, hydroxyethyl methacrylate and benzyl methacrylate have an epoxy ring which is reactive and is also carbon-carbon-unsaturated. There is a method of reacting a compound having a bonding group (for example, a compound such as glycidyl acrylate) to obtain a target resin. And / or a compound having a reactive isocyanate group and a carbon-to-carbon unsaturated bond group (e.g., isophorone diisocyanate and hydroxyethyl) in the COOH group of the terpolymer of dicyclopentenyl acrylate, methacrylic acid and styrene Compounds such as equimolar reactants of methacrylate) and the like to obtain a target resin. In reaction with an OH group, the compound which has an acid anhydride, an isocyanate group, and an acryloyl group can also be used besides an epoxy ring. Moreover, saturated or unsaturated polybasic acid anhydride is reacted with the compound obtained by making unsaturated carboxylic acid, such as acrylic acid, react with the compound which has the epoxy ring of Unexamined-Japanese-Patent No. 6-102669 and 6-1938. The reactant obtained by making it can also be used.

Although the structure of alkali-soluble resin of this invention is shown to the following (specific example 1), for example, this invention is not limited to this.

Embodiment 1

3000-50000 are preferable and, as for the molecular weight of alkali-soluble resin of the said invention, 5000-20000 are more preferable. As for the structural unit ratio of the said specific example 1, l: m: n: o [molar ratio] = 5-70: 5-60: 5-60: 5-70 are preferable, Especially 10-60: 10-50: 10 50: 10-60 are preferable, Most preferably, it is 15-50: 10-40: 10-40: 15-50.

As content in the photocurable coloring composition of the acryl-type copolymer which concerns on this invention, 1-20 mass% is preferable with respect to the total mass of a photocurable coloring composition, and 5-15 mass% is more preferable. When the content is within the above range, even when the concentration of the coloring agent is increased, high sensitivity can be maintained, the development speed can be optimized, and good development performance can be obtained, and the tack time of the process can be shortened.

-coloring agent-

 The photocurable coloring composition of this invention contains at least 1 sort (s) of a coloring agent. By containing a coloring agent, the visual image of a desired color can be formed.

 Although content of the coloring agent in this invention changes also with a kind, color, etc. of a coloring agent, 30 mass% or more is normally preferable with respect to the total mass of the nonvolatile component in a photocurable coloring composition. Moreover, although there is no restriction | limiting in particular as the upper limit, 75 mass% or less is preferable.

Moreover, when a coloring agent is black (BM), 47 mass% or more is preferable, 50 mass% or more is more preferable, 55 mass% or more and 75 mass% or less are more preferable. In the case of red (R), 30 mass% or more is preferable, 33 mass% or more is more preferable, 35 mass% or more and 70 mass% or less are more preferable. In the case of green (G), 45 mass% or more is preferable, 48 mass% or more is more preferable, 50 mass% or more and 70 mass% or less are more preferable. Moreover, in the case of blue (B), 30 mass% or more is preferable, 32 mass% or more is more preferable, 35 mass% or more and 70 mass% or less are more preferable. When the content rate of the coloring agent in a photocurable coloring composition is high, it is hard to reach the lowest part of a to-be-exposed layer by ultraviolet rays (especially 365 nm) used as exposure light by absorption of a coloring agent. For this reason, the lowermost part of the to-be-exposed layer is insufficiently hardened by exposure, so that the description in development is difficult to be obtained, and furthermore, the development margin is small or the development latitude can be reduced. Depending on the kind of coloring agent (RGB and black (BM)), the absorbance (exposure degree of hardening of the said colored layer lowest) of exposure light differs. This invention exhibits an effect especially when content of a coloring agent is large. In particular, the effect is great when the colorant is black. According to this invention, when the coloring power is high (hence high color purity) and black is used as a coloring agent, the composition coating film with favorable light-shielding property can be obtained. Moreover, the coating film has high sensitivity, and developability with better development margin and development latitude is obtained.

In addition, said "non-volatile content" means the solid component which remains as a coating film on a board | substrate after forming a photocurable coating film on the board | substrate other than the solvent in a photocurable coloring composition, ie, drying and solidifying on a board | substrate.

It does not specifically limit as a coloring agent, Both the coloring agent of colored pigments, such as R, G, and B which form the color pixel of a color filter, and the black coloring agent generally used for black matrix formation can be used.

In the present invention, when the photocurable coloring composition is constituted by using a black colorant, the effect of the present invention, namely, high sensitivity can be obtained, and the development margin and the development latitude are more excellent in developability. Exerted highly. Therefore, as a coloring agent, a black coloring agent is preferable and it is preferable also to RGB with large color purity.

As a black coloring agent, carbon black, titanium black, graphite, iron oxide, titanium oxide, and these pigments and dyes mentioned later are mentioned, It does not specifically limit. Especially, carbon black, titanium black, and graphite are preferable, and carbon black is more preferable. These can use 2 or more types together in addition to using individually by 1 type.

As a mass ratio (mass of carbon black: mass of the coloring agent used together), when using 2 or more types together, the range of 95: 5-60: 40 is preferable, 95: 5-70: 30 is more preferable, 90:10 80:20 is more preferable. In the case of plural black colorants, the plural total masses are obtained. If the mass ratio is within the above range, there can be formed a stable coating film without aggregation of the dispersion and non-uniformity.

Carbon blacks include, for example, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # 650 from Mitsubishi Chemical Corporation , MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, DIABLACK A, DIABLACK N220M, DIABLACK N234, DIABLACK I, DIABLACK LI, DIABLACK II, DIABLACK N339, DIABLACK SH, DIABLACK SHA, DIABLACK LH, DIABLACK H, DIABLACK HA, DIABLACK SF, DIABLACK N550M, DIABLACK E, DIABLACK G, DIABLACK R, DIABLACK N760M, DIABLACK LP; Cancarb Ltd. Carbon Black Thermal Series N990, N991, N907, N908, N990, N991, N908; Asahi Carbon Co, Ltd. Carbon Black Asahi # 80, Asahi # 70, Asahi # 70L, AsahiF-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal; Degsa Co. Product Carbon Black Color Black Fｗ200, Color Black Fｗ2, Color Black Fｗ2V, Color Black Fｗ1, Color Black Fｗ18, Color Black S170, Color Black S160, Special Black 6, Special Black 5, Special Black 4, Special Black 4A, Printex U , PrintexV, Printex 140U, Printex 140V, and so on.

It is preferable that carbon black has insulation. Insulating carbon black is carbon black which shows insulation property when the volume resistance is measured by powder as described below. For example, carbon black has an organic substance adsorbed, coated or chemically bonded (grafted) to the surface of carbon black particles. It means having an organic compound on the black particle surface.

In the above, the copolymer (mass average molecular weight 30,000) which copolymerized carbon black, benzyl methacrylate, and methacrylic acid in a molar ratio of 70:30 is dispersed in propylene glycol monomethyl ether so that it may become 20:80 mass ratio, and a coating liquid Was prepared and coated on a chromium substrate with a thickness of 1.1 mm and 10 cm x 10 cm to produce a coating film having a dry film thickness of 3 µm, after which the coating film was heat-treated in an oven at 200 ° C. for 1 hour, according to JIS K 6911. When applied to a high resistivity meter Hiresta-UP (MCP-HT450, manufactured by Mitsubishi Chemical Corporation) and the volume resistivity was measured under an environmental condition with a temperature of 23 ° C. and a relative humidity of 65%, the volume resistivity was 10 ⁶ Pa · cm or more, More preferably, carbon black of 10 ⁸ Pa · cm or more, particularly 10 ⁹ Pa · cm or more, is preferable.

As carbon blacks other than the above, for example, Japanese Patent Laid-Open No. 11-60988, Japanese Patent Laid-Open No. 11-60989, Japanese Patent Laid-Open No. 10-330643, Japanese Patent Laid-Open No. 11-80583 and Japanese Patent The resin-coated carbon black disclosed in Unexamined-Japanese-Patent No. 11-80584, Unexamined-Japanese-Patent No. 9-124969, and Unexamined-Japanese-Patent No. 9-95625 can be used. In addition, what disperse | distributed carbon black to resin suitably may be sufficient.

In order to disperse carbon black in resin, carbon black is added to a dispersion resin and a solvent to form a mill base, which is flashed, kneader, ball mill, sand mill, bead mill, 2 or 3 roll mill, extruder, paint shaker, and ultrasonic disperser. And dispersion treatment by a homogenizer or the like. These treatment methods can also be combined 2 or more. In order to disperse | distribute carbon black uniformly, a dispersing agent can be used as needed.

Examples of the dispersant include a hydrophilic portion such as a carboxyl group, an OH group, a sulfonic acid group, a phosphoric acid group, an amino group, a carbonyl group, and a polyoxyalkylene moiety, and a lipophilic portion such as a phenyl group (including a naphthalene ring), an alicyclic ring, an alkyl group, and a group in which they are substituted Although a compound having a compound, a hydrophilic part having a pigment-like structure and / or a compound having a lipophilic part, and the like are generally used as a dispersant, the compounds exemplified below can be used. However, the said dispersing agent is not limited to these compounds.

For example, EFKA-1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 5070, 5207 (above EFKA ADDITIVES), Anti-Terra-U, Anti-Terra-U100, Anti-Terra-204, Anti-Terra -205, Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151, P-104, P-104S, P105, 220S, 203, 204, 205, 9075 , 9076, 9077 (by BYK Corporation), Disparlon 7301, 325, 374, 234, 1220, 2100, 2200, KS260, KS273N, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN470, 472, 480, 482, K-SPERSE131, 152, 152MS (above Kusumoto Chemicals, Ltd. product), Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, etc. (AVECIA Products), CARRYBON B, Copper L-400, Eleminol MBN-1, Sanspal PS-2, Copper PS-8, IONET S-20 (manufactured by Sanyo Chemical Industries, Ltd.) Disperse Aid 6, Disperse Aid 8, Disperse Aid 15 , Disperse Aid 9100 (SAN NOPCO LIMITED) Etc. can be used. These may be used independently and may use 2 or more types together. The addition amount of a dispersing agent is 3-30 mass parts with respect to a pigment, Preferably it is 5-20 mass parts.

Moreover, a dispersion resin can also be used as needed. By using a dispersion resin, dispersion stability and preservation are improved. As a specific example of a dispersion resin, resin which has a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, etc. is preferable. As a polymer which has a carboxylic acid in a side chain, For example, Unexamined-Japanese-Patent No. 59-44615, Unexamined-Japanese-Patent No. 54-34327, Unexamined-Japanese-Patent No. 58-12577, Unexamined-Japanese-Patent No. 54-25957, for example Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid such as those described in Japanese Patent Application Laid-Open No. 59-53836 and Japanese Patent Laid-Open No. 59-71048 Copolymers, partially esterified maleic acid copolymers, and the like, as well as acidic cellulose derivatives having a carboxylic acid in the side chain. These include, for example, monomers having carboxyl groups such as (meth) acrylic acid, (maleic anhydride), crotonic acid, itaconic acid, fumaric acid, styrene, α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) Propyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl Ether, ethyl acrylate glycidyl, crotonic glycidyl ether, (meth) acrylic chloride, benzyl (meth) acrylate, phenyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-metholacrylamide Polymers copolymerized with one or more copolymerization components such as N, N dimethyl acrylamide, N-methacryloyl morpholine, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminoethyl acrylamide Are listed. Among them, preferred is a (meth) acrylic resin containing at least (meth) acrylic acid or (meth) acrylic acid alkyl ester as the constituent monomer, and a (meth) acrylic resin containing (meth) acrylic acid and styrene is also preferable. These acrylic copolymer components are not limited to the above.

Moreover, these resin can also add ethylenic double bond to a side chain. By providing a double bond to a side chain, photocurability can be improved and resolution and adhesiveness can be improved further.

As a synthetic means which introduce | transduces an ethylenic double bond, the method as described in Unexamined-Japanese-Patent No. 50-34443, Unexamined-Japanese-Patent No. 50-34444, etc. are mentioned, for example. Specifically, the method of making a carboxyl group and a hydroxyl group react with the compound which has glycidyl group, an epoxy cyclohexyl group, and a (meth) acryloyl group, acrylic acid chloride, etc. are mentioned. For example, (meth) acrylic acid glycidyl, allylglycidyl ether, α-ethylacrylic acid glycidyl, crotonylglycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) Resin which has a polymerization group in a side chain can be obtained by making it react with resin which has a carboxyl group or a hydroxyl group using compounds, such as methyl (meth) acrylate, (meth) acrylic acid chloride, and (meth) aryl chloride. Especially as resin which has the said carboxyl group and a hydroxyl group, resin which made (3, 4- epoxycyclohexyl) methyl (meth) acrylate reacted is preferable. Specific examples of these compounds include, for example, the Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic acid oligomer, Diamond Sharmrock Co. Ltd., BISCOAT R-264, KS RESIST 106). (All from Osaka Organic Chemical Industry Ltd.), CYCLOMER P series, PLACCEL CF 200 series (all from Daicel Chemical Industries, Ltd.), Ebecryl 3800 (from DAICEL-UCB COMPANY LTD), and the like.

Moreover, the polymer obtained by the copolymerization reaction of the monomer represented by the following general formula [I] and the monomer which has an acidic group at least (the said copolymerization component can be enumerated) can also be used as resin which has the said carboxyl group and a hydroxyl group.

In the general formula [I], R represents a hydrogen atom or a methyl group, and R ₁ to R ₅ each independently represent a group selected from a hydrogen atom, a halogen atom, a cyano group, an alkyl group and an aryl group.

Specific examples of the halogen atom include Cl, Br, I and the like. The alkyl group may be linear, branched or cyclic, and examples thereof include a methyl group, n-propyl group, iso-propyl group, tert-butyl group and the like, and preferably have 1 to 7 carbon atoms. As said aryl group, a phenyl group, a furyl group, a naphthyl group, etc. are mentioned, for example.

In the above, various monomers are selected as the dispersing resin, and so that the solubility and the acid value can be adjusted, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferable.

The preferable range of the weight average molecular weight (mass average molecular weight) measured by the gel permeation chromatography (GPC) of these dispersion resins is 1,000-80,000, More preferably, it is 3,000-50,000, Most preferably, it is 3,000-20.000. By setting it as 80,000 or less, favorable dispersibility and fluidity | liquidity of a liquid are obtained, and favorable developability is obtained.

These resins can be used not only for dispersion but also for preparing a resist. When preparing a resist, it is preferable to add the following epoxy resin in addition to the said resin.

In preparing the resist, the following epoxy resins can be added to the dispersion resin. As said epoxy resin, it is a compound which has 2 or more epoxy rings in a molecule | numerator, such as bisphenol A type, a cresol noblock type, a biphenyl type, and an alicyclic epoxy compound. For example, as bisphenol A, EPOTOTE YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Toto Chemical Co.), DENACOL Ex-1101, Ex-1102, Ex-1103 and the like (above Nagase Chemical Ltd.), PLACCEL GL-61, GL-62, G101, G102 (above, Daicel Chemical Industries, Ltd. And similar bisphenol F-type and bisphenol S-type. In addition, epoxy acrylates such as Ebecryl 3700, 3701, 600 (above, manufactured by DAICEL-UCB COMPANY LTD.) Can also be used. As the cresol noblock type, EPOTOTE YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Toto Chemical Co.), DENACOL EM-125, etc., (made by Nagase Chemical Ltd.) As the biphenyl type, alicyclic epoxy compounds such as 3,5,3 ', 5'-tetramethyl-4,4'-diglycidyl biphenyl, such as Celoxide 2021, 2081, 2083, 2085, EPOLIDE GT-301 , GT-302, GT-401, GT-403, EHPE-3150 (above, manufactured by Daicel Chemical Industries, Ltd.), SUNTOHTO ST-3000, ST-4000, ST-5080, ST-5100, etc. (above, Tohto Kasei Co., Ltd.), Epiclon 430, 673, 695, 850S, 4032 (above Dainippon Ink & Chemicals, Incorporated), and the like. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyl tris (hydroxyethyl) isocyanurate, o Phthalic acid diglycidyl ester, telephthalic acid diglycidyl ester, and other glycidyl esters in which the dimer acid is modified in the skeleton of the amine epoxy resins EPOTOTE YH-434, YH-434L, and the bisphenol A epoxy resin. Can be used.

Among these, the preferable epoxy resin has "molecular weight / number of epoxy rings" of 100 or more, and 130-500 are more preferable. If the "molecular weight / number of epoxy rings" is small, the curability is high, the shrinkage upon curing is large, and if too large, the curability is insufficient, the reliability is insufficient, or the flatness is poor. Specific preferred compounds include EPOTOTE YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, PLACCEL GL-61, GL-62, 3,5,3 ', 5'-tetramethyl-4, Although 4'- diglycidyl biphenyl, Celoxide 2021, 2081, EPOLIDE GT-302, GT-403, EHPE-3150, etc. are mentioned, these are "the number of molecular weight / epoxy ring" 135-350.

These dispersants may be used alone or in combination of two or more. By dispersing, the resin is adsorbed on the surface of the pigment and the carbon black, and at the same time, the aggregation of the pigment and the carbon black particles is destroyed, and the particle diameter is reduced.

In the present invention, examples of the pigment and carbon black dispersed in the resin or the like include powder, paste shape, pellet shape, paste shape, sheet shape and the like.

The average particle diameter of the pigment and carbon black dispersed in the resin or the like is in the range of 0.003 to 0.5 m, more preferably in the range of 0.005 to 0.3 m, particularly preferably 0.01 to 0.15 m. Thereby, the various effects of the present invention, in particular, developability and development reproducibility are further excellent.

As a pigment used as a coloring agent, such as RGB, an inorganic pigment or an organic pigment can be used. In addition, considering that it is preferable that the pigment has a high transmittance regardless of inorganic or organic, it is preferable to use a pigment having a small particle size and a small particle size as much as possible from the viewpoint of handling.

Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like, and specifically, metal oxides and metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Complex oxides may be enumerated.

As the organic pigment

C.I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;

C.I. Pigment Orange 36, 38, 43, 71;

C.I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;

C.I. Pigment Violet 19, 23, 32, 39;

C.I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment Green 7, 36, 37;

C.I. Pigment Brown 25, 28;

C.I. Pigment Black 1, 7;

And the like.

Especially in this invention, what has basic N atom in the structural formula of a pigment can be used preferably. Pigments having these basic N atoms exhibit good dispersibility in the compositions of the present invention. Although the cause is not elucidated sufficiently, it is presumed that the favorable affinity of the photosensitive polymerization component and a pigment is having an influence.

The following are mentioned as a more preferable pigment among the said pigments. However, it is not limited to these.

C.I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185;

C.I. Pigment Orange 36, 71;

C.I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264;

C.I. Pigment Violet 19, 23, 32;

C.I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;

C.I. Pigment Green 7, 36, 37;

C.I. Pigment Black 1, 7

Organic pigments may be used alone or in combination, in order to increase color purity. A specific example is shown below.

Examples of the red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or mixed pigments in combination of these red pigments, at least one of them and disazo yellow pigments, isoindolin yellow pigments, A mixed pigment of a quinophthalone yellow pigment and the like can be used.

For example, the anthraquinone pigments include C.I. Pigment Red 1 77 is a C.I. Pigment Red 155, C.I. Pigment Red 224 is a diketopyrrolopyrrole pigment, C.I. Pigment Red 254 is enumerated, and C.I. Pigment Yellow 83 or C.I. Good mixing of Pigment Yellow 139. As for the mass ratio of a red pigment and a yellow pigment, 100: 5-100: 50 were favorable. If it is less than 100: 5, the light transmittance of 400-500 nm cannot be suppressed and color purity may not be improved. In addition, if it exceeds 100: 50, the dominant wavelength becomes shorter and the deviation from the NTSC target color becomes larger. Especially, the range of 100: 10-100: 30 is optimal. In the case of the combination of red pigments, it adjusts according to chromaticity.

Examples of the green pigments include halogenated phthalocyanine pigments alone or a mixture of these and disazo yellow pigments, quinophthalone yellow pigments, azomethine yellow pigments or isoindolin yellow pigments, for example C.I. Pigment Green 7, 36 or 37 and C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180 or C.I. Good mixing of Pigment Yellow 185. The mass ratio of the green pigment and the yellow pigment is preferably 100: 5 to 100: 150. If less than 100: 5, the light transmittance of 400-450 nm cannot be suppressed and color purity cannot be improved. In addition, when it exceeds 100: 150, the dominant wavelength becomes long and the deviation from the NTSC target color becomes large. A more preferable mass ratio is the range of 100: 30-100: 120.

As the blue pigment, a phthalocyanine-based pigment alone or a mixture of this and a dioxazine-based purple pigment is used, for example, C.I. Pigment Blue 15: 6 and C.I. Good mixing of Pigment Violet 23. As for the mass ratio of a blue pigment and a purple pigment, 100: 0-100: 30 are preferable, More preferably, it is 100: 10 or less.

In addition, a pigment-containing photocurable resin composition having good dispersibility and dispersion stability can be obtained by using a powdery processing pigment in which the pigment is finely dispersed in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, or the like. have. The pigment in this invention is not limited to the pigment species illustrated above.

When using dye as a coloring agent, the photocurable coloring composition melt | dissolved uniformly is obtained.

There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. Hei 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Japanese Patent Registration No. 2592207, US Patent 4,808,501, 5,667,920, 5,059,500, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115, Japan Japanese Patent Laid-Open No. 6-194828, Japanese Patent Laid-Open No. 8-211599, Japanese Patent Laid-Open No. 4-249549, Japanese Patent Laid-Open No. 10-123316, Japanese Patent Laid-Open No. 11-302283, Japan Japanese Patent Laid-Open No. 7-286107, Japanese Patent Laid-Open No. 2001-4823, Japanese Patent Laid-Open No. 8-15522, Japanese Patent Laid-Open No. 8-29771, Japanese Patent Laid-Open No. 8-146215, and Japanese Patent Japanese Patent Laid-Open No. 11-343437, Japanese Patent Laid-Open No. 8-62416, Japanese Patent Publication 2002-14220, Japanese Patent Publication 2002-14221, Japanese Patent Publication 2002-14222, Japanese Patent Publication 2002-14223, Japanese Patent Application Laid-Open No. 8-302224, Japanese Patent Application Laid-Open No. 8- It is a pigment | dye as described in Unexamined-Japanese-Patent No. 73758, Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531.

Chemical structures include pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, and phenothia Dyestuffs such as true, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used.

Polymerizable Compound

The photocurable coloring composition of this invention contains at least 1 sort (s) of a polymeric compound. A polymeric compound receives the action | action of the active species from the photoinitiator mentioned later, and polymerizes and image-forms.

As a polymeric compound, the compound which has at least 1 ethylenically unsaturated group whose boiling point is 100 degreeC or more in a normal pressure state is preferable, and the tetrafunctional or more than 4 functional acrylate compound is especially preferable.

Examples of the compound having at least one ethylenically unsaturated group having a boiling point of 100 ° C. or higher in an atmospheric pressure state include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate. Monofunctional acrylate or methacrylate; Polyethylene glycol di (meth) acrylate, trimetholethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimetholethane (Meth) acrylated after addition of ethylene oxide or propylene oxide to the polyfunctional alcohol of; poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Urethane acrylates described in Japanese Patent Application Laid-Open No. 50-6034, Japanese Patent Application Laid-open No. 51-37193, and Japanese Patent Publication No. 48-64183 Polyfunctional acrylates, such as the polyester acrylates of Unexamined-Japanese-Patent No. 49-43191, 52-30490, and epoxy acrylate which is a reaction product of an epoxy resin and (meth) acrylic acid Methacrylate is listed.

Moreover, what was introduced as a photocurable monomer and oligomer can be used by Japanese adhesive association Vol.20, No.7, pages 300-308.

In addition, after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in Japanese Patent Application Laid-open No. Hei 10-62986 together with the specific examples as general formulas (1) and (2), (meth) acrylated Compounds can also be used.

Especially, the structure in which dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these acryloyl groups via ethylene glycol and a propylene glycol residue are preferable. These oligomer types are also used.

A polymeric compound can be used individually by 1 type or in combination of 2 or more types.

As content in the photocurable coloring composition of a polymeric compound, it is 20-200 parts preferably with respect to 100 parts of photocurable coloring compositions (total solid content), More preferably, it is 50-120 parts. If the said content is in the said range, hardening will be performed favorably.

Photoinitiator

The photocurable coloring composition of this invention contains at least 1 sort (s) of a photoinitiator. By using a photoinitiator, a higher degree of hardening is obtained and it is also possible to control curability as desired.

As a photoinitiator, active halogen compounds, such as a halomethyloxadiazole compound and a halomethyl-s-triazine type-compound, 3-aryl substituted coumarin compound, at least 1 type of lophine dimer, etc. can be mentioned, for example.

Among the active halogen compounds, as the halomethyloxadiazole compound, for example, 2-halomethyl-5-vinyl-1,3,4-oxa represented by General Formula IV described in Japanese Patent Publication No. 57-6096 Diazole compounds and the like.

 Specific examples of the 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole and 2-trichloro Methyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole and the like Listed.

As said halomethyl-s-triazine type compound, For example, the vinyl-halomethyl-s-triazine compound represented by General formula V of Unexamined-Japanese-Patent No. 59-1281, Unexamined-Japanese-Patent No. 53-133428 2- (naphtho-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by formula VI described in the above and 4- (p-aminophenyl) -2 represented by formula VII , 6-di-halomethyl-s-triazine compound and the like.

Specific examples of the vinyl-halomethyl-s-triazine compound include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine and 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like This is listed.

Specific examples of the 2- (naphtho-1-yl) -4,6-bis-halomethyl-s-triazine compound include 2- (naphtho-1-yl) -4,6-bis-trichloromethyl -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphtho-1- Yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -[4- (2-methoxyethyl) -naphtho-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxy ethyl) -naphtho -1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxy ethyl) -naphtho-1-yl] -4,6-bis-trichloro Methyl-s-triazine, 2- (2-methoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5-methyl- Naphto-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphtho-2-yl) -4,6-bis-trichloromethyl-s -Triazine, 2- (5-methoxy-naphtho-1-yl) -4,6-bis-trichloro Methyl-s-triazine, 2- (4,7-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphtho 2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-s -Triazine and the like.

Specific examples of the 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound include 4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-tri Azine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) Aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- ( pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- (pN-chloroethyl carbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) car Bonylaminophenyl] 2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di ( Oxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2 , 6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s -Triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bro Parent-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycar Bonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6- Di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4 -[o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-tri Ajin,

4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (Chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di ( Trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- ( m-bromo-pN-ethoxycarbonylmethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethyl aminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine , 4- (o-bromo-pN-ethoxycarbonylmethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethyl Aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluor -pN-ethoxycarbonylmethyl aminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di ( Trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN -Chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylamino Phenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6- [3-bromo-4- [N, N-bis (ethoxycarb) Bonylmethyl) amino] phenyl] -1,3,5-triazine and the like.

Particularly preferred of the 3-aryl substituted coumarin compounds are {(s-triazin-2-yl) amino} -3-aryl coumarin compounds.

The ropin dimer refers to a 2,4,5-triphenylimidazolyl dimer made from two lopin residues.

Specific examples include 2- (o-crophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- ( o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4, 5-diphenylimidazolyl dimer etc. are mentioned.

Other known initiators may be used in addition to the photopolymerization initiator.

Bisinal polyketolaldonyl compounds described in US Pat. No. 2,367,660, α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670, Acyl Inether described in US Pat. No. 2,448,828, US Pat. Aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, triarylimidazole dimers described in US Pat. No. 3,549,367. The combination of p-aminophenyl ketone and the benzothiazole type compound / trihalomethyl-s-triazine type compound of Unexamined-Japanese-Patent No. 51-48516 etc. are mentioned.

In addition, Adekaoptomer SP-150, East 151, East 170, East 171, East N-1717, East N1414, etc. (above, manufactured by Asahi Denka Kogyo Co., Ltd.), OXE-01, OXE-02, CGI113, IR379, IR369, IR907, IR184, IR819 (above Ciba Specialties Chemicals Co. Ltd.), etc. can also be used as a photoinitiator.

As content in the photocurable coloring composition at the time of containing a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of the said composition, More preferably, it is 0.5-5.0 mass%. When content of a photoinitiator is in the said range, superposition | polymerization hardening can be performed favorably and high film strength can be obtained.

The following sensitizers can be used together for a photoinitiator. Specific examples include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10- Anthraquinone, xanthone, 2-methyl xanthone, 2-methoxyxanthone, 2-ethoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyrylketone, p- (dimethylamino ) Phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) benzophenone (or miher ketone), p- (diethylamino) benzophenone, benzanthrone, 7- {L-4-chloro -6- (diethylamino) -S-triazinyl (2), 1-amino} -3-phenylcoumarin, etc., the benzothiazole type compound of Unexamined-Japanese-Patent No. 51-48516, etc. are mentioned.

In addition, when the pigment concentration is increased to create high color purity, the thixotropy of the coating liquid is generally increased, and thus, the film thickness non-uniformity easily occurs after coating, and in particular, the slit coat method allows leveling of the liquid until drying to achieve uniform thickness. It is important to form a coating film. For this reason, it is preferable to contain an appropriate surfactant in the said colored photosensitive resin composition.

As said surfactant, surfactant disclosed by Unexamined-Japanese-Patent No. 2003-337424 and Unexamined-Japanese-Patent No. 11-133600 is mentioned as a preferable thing.

As surfactant for improving applicability | paintability, a nonionic surfactant, a fluorine-type surfactant, a silicone type surfactant, etc. are added.

Examples of the nonionic surfactants include polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, and polyoxypropylene alkyl ethers. And nonionic surfactants such as polyoxypropylene alkylaryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters are preferable. Specifically, Polyoxyalkylene glycol, such as polyoxyethylene glycol and polyoxypropylene glycol; Polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether, polyoxyethylene polythiylated ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene-propylene polytyrylated ether and polyoxyethylene nonylphenyl ether; And nonionic surfactants such as polyoxyalkylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters, and polyoxyalkylene sorbitan fatty acid esters. Specific examples thereof include, for example, ADEKA Pluronic series, ADEKA NOL series, Tetronic series (above, ADEKA Corporation), EMALGEN series, REODOL series (above, Kao Corporation), ELEMINOL series, NONIPOL series, OCTAPOL series, DODECAPOL series, NEWPOL series (above, Sanyo Chemical Industries, Ltd.), Pionine series (above, Takemoto Oil & Fat Co., Ltd.), Nissan Nonion series (above, Nippon Oil and Fats Co., Ltd.) . Those commercially available can be used suitably. Preferable HLB value is 8-20, More preferably, it is 10-17.

As the fluorine-based surfactant, a compound having a fluoroalkyl or a fluoroalkylene group in at least one of terminal, main chain and side chain can be suitably used. Specific commercially available products include, for example, Megafac F142D, Copper F172, Copper F173, Copper F176, Copper F177, Copper F183, Copper 780, Copper 781, Copper R30, Copper R08 (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorade FC-135 , East FC-170C, East FC-430, East FC-431 (Sumitomo 3M Co., Ltd., Products), Surflon S-112, East S-113, East S-131, East S-141, East S- 145, East S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (manufactured by Asahi Glass Co., Ltd.), Eftop EF 351 , 352, 801, 802 (manufactured by JEMCO Corporation).

As said silicone type surfactant, Toray Silicone DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF-8428, DC-57, DC-190 (above, manufactured by Toray Dowcorning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicones Co., Ltd.) etc. can be mentioned.

These surfactants are preferably 5 parts by mass or less, more preferably 2 parts by mass or less with respect to 100 parts by mass of the resist liquid. When the amount of the surfactant exceeds 5 parts by mass, surface cracks are likely to occur in coating and drying, and smoothness is likely to deteriorate.

-solvent-

Generally the preparation of the photocurable coloring composition of this invention can be suitably performed using a solvent. Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters and methyl lactate Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethyl ethoxy acetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate such as methyl 3-methoxy propionate, ethyl 3-methoxy propionate, methyl 3-ethoxy propionate and ethyl 3-ethoxy propionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionic acid, such as methyl 2-propionate, ethyl 2-methoxy propionate, 2-methoxy propionic acid, 2 Methyl ethoxy propionate, ethyl 2-ethoxy propionate, methyl 2-oxy-2-methyl propionate, ethyl 2-oxy-2-methyl propionate, methyl 2-methoxy-2-methyl propionate, 2-ethoxy-2 Ethyl ethyl propionate; Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, acet acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate; dipropylene glycol monomethylether acetate, propylene glycol n-butylether acetate, diethylene glycol Monoethyl ether acetate, tripropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, dipropylene glycol n-propyl ether acetate, propylene carbonate, diethylene glycol monobutyl ether acetate, dipropylene glycol n-butyl ether acetate Propylene glycol phenyl ether acetate, triacetin, tripropylene glycol n-butyl ether acetate, triacetin monoacetate, triacetin diacetate, and the like; And ethers such as diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, dipropylene glycol monon-butyl ether, diethylene glycol monobutyl ether, tripropylene glycol monon-butyl ether, tetrahydrofuran, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol Ethyl ether acetate, propylene glycol propylether acetate, and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; Aromatic hydrocarbons such as toluene, xylene and the like.

Of the above, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone , Ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, butylene glycol diacetate and the like are preferable. You may use a solvent in combination of 2 or more type other than using individually by 1 type.

Other Ingredients

The photocurable coloring composition of this invention mix | blends various additives, such as a filler, a high molecular compound other than the said alkali-soluble resin, surfactant other than the above, an adhesion promoter, antioxidant, a ultraviolet absorber, an anticoagulant, etc. as needed other than the said component. can do.

Specific examples of the various additives include fillers such as glass and alumina; Vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyl dimethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, (meth)) acryloyl propyltrimethoxysilane, (meth) acryloyl propyltriethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, 3-chloropropyl methyldimethoxysilane, 3-chloropropyl trimethoxysilane Adhesion promoters such as 3-methacryloxypropyl trimethoxysilane and 3-mercaptopropyl trimethoxysilane; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; And ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

Moreover, when promoting alkali solubility of an uncured part and further improving developability of a photocurable coloring composition, organic carboxylic acid, Preferably the low molecular weight organic carboxylic acid of 1000 or less molecular weight can be performed.

Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, capric acid, diethyl acetic acid, enanthic acid and caprylic acid; Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fimeric acid, sveric acid, azelaic acid, sebacic acid, brazilian, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarbali acid, acotinic acid and camphoric acid; Aromatic mono carboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Phenyl Acetate, Phenoxy Acetic Acid, Methoxyphenoxy Acetate, Hydroatroic Acid, Hydrocinnamic Acid, Mandelic Acid, Phenyl Succinic Acid, Atropic Acid, Cinnamic Acid, Methyl Cinnamic Acid, Cinnamic Acid Benzyl, Cinnamylidene Acetic Acid, Coumalic Acid And other carboxylic acids such as Unberic acid.

It is preferable to further add a thermal polymerization inhibitor to the photocurable coloring composition of this invention in addition to the above. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone and 4,4-thiobis (3-methyl-6-t-butylphenol), 2,2-thiobis (4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole and the like are useful.

Preparation of Photocurable Coloring Composition

The photocurable coloring composition of the present invention is a mixture of a colorant, an acrylic copolymer (alkali soluble resin) according to the present invention, a polymerizable compound and a photopolymerization initiator and other components (preferably with a solvent) as necessary, and various mixers. It can prepare by mixing-dispersing using the dispersing machine.

In addition, the step of mixing and dispersing (mixing and dispersing step) is preferably constituted by kneading dispersion and undispersed treatment carried out subsequently, but it is also possible to omit kneading dispersion. In addition, it is preferable that the pigment species used for the kneading and dispersing steps be made to have a smaller particle size in advance by salt milling or the like. Salt milling methods are known from Japanese Patent No. 3130217, Japanese Patent Publication No. 2003-504480, and the like. Moreover, the pigment of microparticles | fine-particles formed by the buildup method can also be used.

In the kneading and dispersing step, the surface of the colorant of the raw material is promoted the wettability with the constituents mainly composed of the vehicle resin component, and is converted from the solid / gas interface of the colorant particles and air to the solid / solution interface of the colorant particles and the vehicle solution. . In the microdispersion step, the colorant particles are dispersed to a minute state close to the primary particles by mixing and stirring together with the medium for dispersing fine particles of glass, zirconium oxide or ceramic. Therefore, in the kneading dispersion step, since the interface formed on the surface of the colorant particles needs to be converted from air to a solution, a strong shear force compressive force is required, and the kneading machine and the kneaded material suitable for it are preferably high viscosity and undispersed. In the process, it is necessary to distribute the particles uniformly and stably to a minute state, and it is preferable that the disperser and the dispersion to which the impacting force and the shearing force are unnecessary on the aggregated colorant particles are relatively low in viscosity.

By using the photocurable coloring composition of the present invention, for example, a kneading dispersion process for producing a color filter, a colorant such as an organic pigment or carbon black, a part of the acrylic copolymer (alkali-soluble resin) according to the present invention and, if necessary, The dispersant or surface treatment agent is kneaded with a portion of the solvent. Machines used for kneading include 2 rolls, 3 rolls, ball mills, tron mills, dispersers, dispersers, kneaders, corneaders, homogenizers, blenders, single screw or twin screw extruders, etc. Disperse while adding Subsequently, the remaining solvent and the acrylic copolymer (alkali-soluble resin; the remainder not used in the kneading) according to the present invention were added, and a 0.01-mm or 1-inch sand grinder, pin mill, slit mill, ultrasonic disperser, or the like was used. It disperse | distributes to the bead which consists of glass of 1 mm diameter, zirconium oxide, etc. It is also possible to omit the kneading step. In this case, a colorant such as a pigment, an acrylic copolymer (alkali-soluble resin) according to the present invention, and a dispersant or a surface treatment agent are beads dispersed together with the solvent, if necessary. In this case, it is preferable to add the acrylic copolymer (alkali-soluble resin) which concerns on this invention as much as it uses when kneading | mixing in the middle of dispersion.

For details on kneading and dispersion, see T.C. Patton Flow and Pigment Dispersion (published by John Wiley and Sons, 1964).

<Color filter>

The color filter of this invention is comprised using the photocurable coloring composition of this invention mentioned above, For example, the photocurable coloring composition prepared in liquid form was apply | coated on a desired board | substrate, a photosensitive layer was formed, and the photocurable layer formed was It can form by exposing to pattern shape and developing. Since the black matrix of this invention is comprised using the photocurable coloring composition mentioned above, black optical density is high and it is comprised by the favorable sharp pattern of a cross-sectional rectangle.

The color filter is generally formed by forming a black matrix which separates a plurality of colored pixels having different colors from the colored pixels. These (particularly black matrices) can be produced by applying the photocurable coloring composition of the present invention on a substrate to form a photocurable layer, drying (prebaking), exposing to a desired pattern, and performing a developing treatment. Can be.

For example, the photocurable coloring composition is applied onto a substrate directly or through another layer by a coating method such as rotary coating, slit coating, flexible coating, roll coating, etc. to form a photocurable layer, which is dried (prebaked) The pattern is exposed through a predetermined photomask, and only the exposed portion is cured, and the operation of removing the unexposed portion with the developer is repeatedly performed by the desired number of colors, such as R, G, B, black, and the like. A color filter formed by forming a coloring image (including a pixel and a black matrix) of three colors or four colors) can be produced.

In this case, the radiation irradiated at the time of exposure is preferably one having a wavelength at 280 to 310 nm, and may have a wavelength other than that, in particular g-ray (436nm), h-ray (405nm), i-ray (365nm), Ultraviolet rays, such as j line | wire (310 nm), are preferable, and ultraviolet rays containing i line | wire and h line | wire are a main component, and j line is preferable. As the light source, an ultra-high pressure mercury lamp can be used, and the exposure machine can be used as a proximity type exposure machine, as a mirror projection method, or as a stepper method.

As for the thickness (after drying) of the photocurable layer which uses a photocurable coloring composition, 0.3-5.0 micrometers is preferable normally, More preferably, it is 0.5-3.5 micrometers, Especially preferably, it is 1.0-2.5 micrometers.

Drying (prebaking) of a photocurable layer can be performed by heating for 10 to 300 second in 50-140 degreeC temperature range in a hotplate, oven, etc. Especially, it is preferable to heat for 60 to 180 second in the temperature range of 70-130 degreeC, and to heat for 90 to 120 second in the temperature range of 90-120 degreeC.

The development treatment is preferably an alkali development treatment, and the uncured portion is eluted in an aqueous alkali solution by exposure, leaving only the photocured cured portion.

As a developing solution, all can be used as long as it melt | dissolves an unhardened part and does not melt the hardened part which comprises a filter part. Specifically, combinations of various organic solvents and alkaline aqueous solutions can be used, and among them, alkaline developer is preferred.

Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. The concentration of the alkaline compounds such as roxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001-10% by mass, preferably 0.01-1 Alkaline aqueous solution dissolved to mass% can be used suitably.

As image development temperature, it is 20-30 degreeC normally, and as image development time, the range of 20-90 second is preferable. In addition, in the case of using a developer composed of such an alkaline aqueous solution, it is generally washed with water after development.

After the developing treatment, a postbaking treatment can be performed as necessary. Post-baking is the post-development heat processing for making hardening perfect, and can normally heat about 200-220 degreeC (hard bake). Post-baking process is performed continuously or collectively using heating means, such as a hotplate, a convection oven (hot air circulation type dryer), and a high frequency heater, so that the layer after image development may be said condition.

Examples of the substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass, which can be used for liquid crystal display devices, and the like, and a transparent conductive film attached thereto, or a photoelectric conversion device substrate that can be used for a solid-state imaging device. For example, a silicon substrate etc. are mentioned. Plastic substrates are also possible. In the case of manufacturing a color filter, a plurality of colored pixels and a black matrix that separates each pixel are usually formed on these substrates.

Raw materials for the plastic substrate include (1) amorphous polyolefin, (2) polyether sulfone, (3) polyglutalimide, (4) polycarbonate, and (5) from optical properties, heat resistance, mechanical strength, etc. Polyethylene terephthalate, (6) polyethylene naphthalate, (7) norbornene polymer, (8) polyimide with bisaniline fluorene as diamine component, (9) polyesters composed of bisphenol fluorene and dibasic acid, and the like. . Among these, (2) polyether sulfone, (4) polycarbonate, (5) polyethylene terephthalate and (7) norbornene polymer are preferable. The raw material is particularly preferable for LCD applications.

The properties required for plastic substrates include low thermal expansion (preventing deterioration of the display accuracy associated with curing treatment when creating color filters), gas barrier properties (securing the stability of liquid crystals), optical properties such as light transmittance and optical isotropy, surface smoothness, etc. There is this. Regarding thermal expansion, the coefficient of thermal expansion is preferably 10 ⁻⁴ or less. In addition, it is preferable that the plastic substrate has a gas barrier layer and / or a solvent-resistant layer on its surface.

The photocurable coloring composition of this invention is suitable for formation of colored pixels of chromatic colors, such as black matrix and RGB which isolate | separate the colored pixel which comprises a color filter.

An overcoat layer (planarization layer) can be formed on the color filter obtained using the photocurable coloring composition of this invention. As resin (OC product) which forms an overcoat layer, an acrylic resin composition, an epoxy resin composition, a polyimide resin composition, etc. are mentioned.

The black matrix formed by using the photocurable coloring composition of the present invention is preferable for liquid crystal display devices (LCDs), and is used for mobile phone terminals such as televisions, PCs, liquid crystal projectors, game machines, mobile phones, digital cameras, and car navigation systems. It can apply preferably without a restriction | limiting in particular.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the meaning is exceeded. In addition, "part" is a mass reference | standard unless there is particular notice.

(Example 1)

Each component of the following composition a was mixed, and it stirred for 8 hours, and obtained the photocurable coloring composition.

<Composition a>

ㆍ pentaerythritol hexaacrylate... Part 4.0

Benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentanyl methacrylate copolymer. Part 2.7

(Copolymerization ratio = 30/40/30 [molar ratio], weight average molecular weight 9,000; acrylic copolymer according to the present invention having a methacryloyl group, a double bond and a cyclopentanyl group in the side chain)

Benzyl methacrylate / methacrylic acid copolymer; 1.0 part

 (Copolymerization ratio = 75/25 [molar ratio], weight average molecular weight about 30,000)

2- (4'-dimethyl-4-biphenyl) -4,6-bis (trichloromethyl) -s-triazine... Part 1.3

Shigenox 102 (manufactured by Hakkol Chemical Inc.). 0.3 part

The following carbon black dispersion liquid. Part 42

Propylene glycol monomethyl ether acetate... Part 48.7

Fluorine-based nonionic surfactant 0.02part

* Carbon Black Dispersion

The following components were dispersed for one day in a sand mill to give a dispersion.

ㆍ Regal 400R (manufactured by Cabot Co.)... Part 27.0

(Average particle size: 31 nm, pH: 9, DBP oil absorption: 42 ml / 100 parts, blackness My value: 235; carbon black)

Benzyl methacrylate / methacrylic acid copolymer; Part 8.0

(Copolymerization ratio = 70/30 [molar ratio], weight average molecular weight about 30,000)

Propylene glycol monomethyl ether acetate... Part 65.0

* Fluorine-based nonionic surfactant

A copolymer of 60% by mass of N-butylperfluorooctane sulfonamide ethyl acrylate and 40% by mass of poly (oxyalkylene) acrylate

(Example 2)

In Example 1, the photocurable coloring composition was prepared by the method similar to Example 1 except having changed composition a into the following composition b.

<Composition b>

ㆍ pentaerythritol hexa acrylate... Part 4.0

Benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentenyl methacrylate copolymer; Part 2.7

(Copolymerization ratio = 30/40/30 [molar ratio], weight average molecular weight 9,000; acrylic copolymer according to the present invention having a methacryloyl group, a double bond and a cyclopentenyl group in the side chain)

Benzyl methacrylate / methacrylic acid copolymer; 1.0 part

(Copolymerization ratio = 75/25 [molar ratio], weight average molecular weight about 30,000)

2- (4'-methyl-4-biphenyl) -4,6-bis (trichloromethyl) -s-triazine... Part 1.3

Shigenox102 (manufactured by Hakkol Chemical Inc.). 0.3 part

The carbon black dispersion liquid; Part 42

Propylene glycol monomethyl ether acetate... Part 48.7

The fluorine-based nonionic surfactant 0.02part

(Example 3)

In Example 1, the photocurable coloring composition was prepared by the method similar to Example 1 except having changed composition a into the following composition c.

<Composition c>-Green photocurable coloring composition

ㆍ pentaerythritol hexa acrylate... Part 2.5

Benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentanyl methacrylate copolymer; Part 1.8

(Copolymerization ratio = 30/40/30 [molar ratio], weight average molecular weight 9,000; acrylic copolymer according to the present invention having a methacryloyl group, a double bond and a cyclopentanyl group in the side chain)

2,4-trichloromethyl (piperonyl) -6-triazine…. 0.5 part

ㆍ IRGACURE 369 (manufactured by Ciba Specialty Chemicals Inc.)... Part 1.4

ㆍ diethyl thioxanthone 0.7 part

To the green dispersion. Part 40.0

Yellow dispersion Part 19.7

Propylene glycol monomethyl ether acetate... Part 33.4

The fluorine-based nonionic surfactant 0.02part

Green dispersion

The following components were dispersed for one day in a sand mill to give a dispersion.

Benzylmethacrylic acid copolymer; Part 9.5

(Copolymerization ratio = 70/30 [molar ratio], weight average molecular weight about 30,000)

ㆍ C.I. Pigment Green 36 (average particle diameter 20 mm in SEM observation). Part 18.0

Propylene glycol monomethyl ether acetate... Part 72.5

* Yellow dispersion

The following components were dispersed for one day in a sand mill to give a dispersion.

Benzylmethacrylic acid copolymer; Part 4.2

(Copolymerization ratio = 70/30 [molar ratio], weight average molecular weight about 30,000)

ㆍ C.I. Pigment Yellow 150 (average particle diameter 25 mm in SEM observation). Part 19.0

Propylene glycol monomethyl ether acetate... Part 76.8

(Comparative Example 1)

In Example 1, the benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentanyl methacrylate copolymer (acrylic copolymer according to the present invention) in the composition a is arylmethacryl. Photocurable coloring composition was prepared by the method similar to Example 1 except having changed into the rate / methacrylic acid (copolymerization ratio = 80/20 [molar ratio], weight average molecular weight 10,000) copolymer.

(Comparative Example 2)

Benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentanyl methacrylate copolymer (acrylic copolymer according to the present invention) in the composition a is The photocurable coloring composition was prepared by the method similar to Example 1 except having changed into the rate / methacrylic acid copolymer (copolymerization ratio = 70/30 [molar ratio], the weight average molecular weight about 30,000).

(Comparative Example 3)

In Example 3, the benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentanyl methacrylate copolymer (acrylic copolymer according to the present invention) in the composition a is arylmethacryl. A photocurable coloring composition was prepared and evaluated in the same manner as in Example 1 except that the rate / methacrylic acid (copolymerization ratio = 80/20 [molar ratio], weight average molecular weight 10,000) was changed to a copolymer.

(Example 4)

In Example 1, the photocurable coloring composition was prepared by the method similar to Example 1 except having changed the composition a into the following composition d.

<Composition d>: Red curable coloring composition

ㆍ 100 parts of red dispersion

4 parts of an acrylic copolymer according to the present invention having a double bond and a cyclopentanyl group

  (Benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentanyl methacrylate copolymer (copolymerization ratio = 30/40/30 [molar ratio], weight average molecular weight 9,000; meta to side chain) Chlorophyll)

ㆍ Alkaline soluble resin 2 parts

  (Propylene glycol monomethyl ether acetate solution (solid content: 50 mass%)) of a benzyl methacrylate / methacrylic acid copolymer (= 75/25 [mass ratio]) copolymer (weight average molecular weight Mw: 10000))

ㆍ Epoxy Resin: (part of product name EHPE 3150 Daicel Chemical Industries, Ltd.)

ㆍ Polymerizable Resin

  (Trade name CYCLOMER P ACA-200, product of Daicel Chemical Industries, Ltd. (50% solution), solid acid value: 118KOHmg / g, double bond equivalent weight: 450g / mol-acrylic)

Polymerizable compound: 6 parts dipentaerythritol hexa acrylate

  (A brand name: DPHA, Nippon Kayaku Co., Ltd. product)

Polymerizable compound: 2 parts of tetra (acryloyloxyethoxy) pentaerythritol

  (A brand name: DP1040, product of Nippon Kayaku Co., Ltd.)

Polymerization initiator A: 1 part of 4- (o-bromo-p-N, N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine

ㆍ Polymerization Initiator B: 1 part of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IR 369, product of Ciba Specialties Chemicals Co. Ltd.)

Polymerization initiator C: 0.5 part of 2,4-diethyl thioxanthone

ㆍ Polymerization inhibitor: 0.01 part of p-methoxyphenol

ㆍ 0.001 part of fluorine-based surfactant

(Product name: Megafac R08, Dainippon Ink & Chemicals, Incorporated)

ㆍ 0.5 parts of nonionic surfactant (trade name: EMALGEN A-60, manufactured by Kao Corporation)

Solvent: 100 parts of propylene glycol methyl ether acetate

Solvent: 70 parts of ethyl 3-ethoxy propionate

* Preparation of Red Dispersion

The following red dispersion composition was stirred for 1 hour using a homogenizer at 3000 rpm. The resulting mixed solution was subjected to microdispersion for 4 hours in a bead disperser (trade name: DISPERMAT, GETZMANN) using 0.1 mm zirconium oxide beads to obtain a dispersion.

(Red dispersion composition)

ㆍ C.I. 25 parts of Pigment Red 254 (average particle size 20 nm in SEM observation)

ㆍ C.I. Pigment Red 177 (average particle diameter 18 nm in SEM observation) 8 parts

ㆍ 20 parts of dispersant

  (Trade name: Disperbyk-161, manufactured by BYK-Chemie GmbH, 30% solution)

ㆍ 11 parts of alkali soluble resin

 Propylene glycol monomethyl ether acetate solution (solid content: 50 mass%) of (benzyl methacrylate / methacrylic acid copolymer (= 75/25 [mass ratio]) copolymer (weight average molecular weight Mw: 10000)

ㆍ 136 parts of propylene glycol monomethyl ether acetate

(Comparative Example 4)

In Example 4, benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentanyl methacrylate copolymer (acrylic copolymer according to the present invention) in composition d is benzyl methacrylate. A photocurable coloring composition was prepared and evaluated in the same manner as in Example 4 except that the acrylate / methacrylic acid copolymer = 75/25 [mass ratio] copolymer and the weight average molecular weight Mw: 10000) copolymer were evaluated. It was.

(Example 5)

In Example 1, the photocurable coloring composition was prepared by the method similar to Example 1 except having changed composition a into the following composition e.

<Composition e> Blue photocurable coloring composition

100 parts of the following blue dispersion liquid

5 parts of an acrylic copolymer according to the present invention having a double bond and a cyclopentanyl group

(Benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentenyl methacrylate copolymer (copolymerization ratio = 30/40/30 [molar ratio], weight average molecular weight 9,000; on the side chain) Methacrylo diary)

ㆍ Epoxy resin: 1 part (trade name EHPE3150, product of Daicel Chemical Industries, Ltd.)

ㆍ 4 parts of polymeric resin

(Brand name: CYCLOMER P ACA-200, product of Daicel Chemical Industries, Ltd. (50% solution), solid dispersion value: 118KOHmg / g, double bond equivalent weight: 450g / mol-acrylic)

ㆍ Polymerizable Compound: 5 parts of dipentaerythritol hexa acrylate

  (A brand name: DPHA, Nippon Kayaku Co., Ltd. product)

Polymerizable compound: 3 parts of tetra (acryloyloxyethoxy) pentaerythritol

  (A brand name: DP1040, product of Nippon Kayaku Co., Ltd.)

Polymerization initiator A: 1 part of 4- (o-bromo-p-N, N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine

ㆍ Polymerization Initiator B: 1 part of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IR 369, product of Ciba Specialties Chemicals Co. Ltd.)

Polymerization initiator C: 0.5 part of 2,4-diethyl thioxanthone

0.2 part of silane coupling agent (N- (2-aminoethyl) -3-aminopropyl trimethoxysilane)

ㆍ Polymerization inhibitor: 0.01 part of p-methoxyphenol

ㆍ 0.001 part of fluorine-based surfactant

  (Brand name: Megafac R30, Dainippon Ink & Chemicals, Incorporated products)

ㆍ 0.5 part of nonionic surfactant (trade name: EMALGENA-60, manufactured by Kao Corporation)

Solvent: 100 parts of propylene glycol methyl ether acetate

Solvent: 50 parts of ethyl 3-ethoxypropionate

* Preparation of Blue Dispersion

The following blue dispersion composition was stirred for 1 hour using a homogenizer at 3000 rpm. The resulting mixed solution was subjected to microdispersion for 4 hours in a bead disperser (trade name: DISPERMAT, GETZMANN) using 0.1 mm zirconium oxide beads to obtain a dispersion.

(Blue dispersion composition)

ㆍ C.I. Pigment blue 15: 6 (average particle diameter 18 nm in SEM observation) 28 parts

ㆍ C.I. Pigment Violet 23 (average particle size 16 nm in SEM observation) 2 parts

ㆍ 10 copies

(Brand name: EFKA4300, EFKA, ADDITIVES product (80% solution))

Alkali-soluble resin: 10 parts of propylene glycol monomethyl ether acetate solutions (solid content: 50 mass%) of the benzyl methacrylate / methacrylic acid copolymer (= 70/30 [mass ratio] copolymer, weight average molecular weight Mw: 8000)

ㆍ 150 parts of propylene glycol monomethyl ether acetate

(Comparative Example 5)

In Example 5, benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentenyl methacrylate copolymer (acrylic copolymer according to the present invention) in composition e is benzyl methacrylate. A photocurable coloring composition was prepared and evaluated in the same manner as in Example 5 except that the acrylate / methacrylic acid copolymer = 75/25 [mass ratio] copolymer and the weight average molecular weight Mw: 10000) copolymer were changed. It was.

Example 6

In Example 1, the photocurable coloring composition was prepared by the method similar to Example 1 except having changed the composition a into the following composition f.

<Composition f> Green photocurable coloring composition

ㆍ 40 parts of green dispersion

ㆍ 20 parts of yellow dispersion

2 parts of an acrylic copolymer according to the present invention having a double bond and a cyclopentanyl group

 (Benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentenyl methacrylate copolymer (copolymerization ratio = 30/40/30 [molar ratio], weight average molecular weight 9,000; on the side chain) Methacrylo diary)

ㆍ Polymerizable Compound: 1.5 parts of dipentaerythritol hexaacrylate

  (A brand name: DPHA, Nippon Kayaku Co., Ltd. product)

ㆍ Polymerizable compounding part: 0.5 part of tetra (acryloyloxyethoxy) pentaerythritol

  (A brand name: DP1040, product of Nippon Kayaku Co., Ltd.)

Polymerization initiator A: 0.8 part of 4- (o-bromo-p-N, N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine

ㆍ Polymerization Initiator D: 1- (9-ethyl-6- (2-methyl benzoyl) -9H-carbazol-3-yl) -1- (O-acetyloxime) ethanone (Ciba Specialties Chemicals Co.Ltd. 1.2

ㆍ Polymerization inhibitor: 0.01 part of p-methoxyphenol

ㆍ 0.001 part of fluorine-based surfactant

  (Product name: Megafac R30, Dainippon Ink & Chemicals, Incorporated)

ㆍ 0.5 part of nonionic surfactant (trade name: EMALGENA-60, manufactured by Kao Corporation)

Solvent: 60 parts of propylene glycol methyl ether acetate

Solvent: 30 parts of ethyl 3-ethoxy propionate

* Preparation of Green Dispersion

The green dispersion B of the following composition was dispersed for one day with a sand mill to obtain a dispersion.

(Green dispersion B)

ㆍ C.I. 18 parts of Pigment Green 36 (average particle size 20mm in SEM observation)

ㆍ 3 parts of dispersant (product name: SOLSPERSE 20000, product of Zeneka Co., Ltd.)

Alkali-soluble resin: 2 parts of propylene glycol monomethyl ether acetate solutions (solid content: 50 mass%) of the benzyl methacrylate / methacrylic acid copolymer (= 70/30 [mass ratio] copolymer, weight average molecular weight Mw: 8000)

ㆍ 77 parts of propylene glycol monomethyl ether acetate

* Preparation of yellow dispersion

The yellow dispersion B of the following composition was dispersed for one day with a sand mill to obtain a dispersion.

(Yellow dispersion B)

ㆍ C.I. 18 parts of Pigment Yellow 150 (average particle size 25mm in SEM observation)

ㆍ 3 parts of dispersant (product name: SOLSPERSE 20000, product of Zeneka Co., Ltd.)

Alkali-soluble resin: 2 parts of propylene glycol monomethyl ether acetate solutions (solid content: 50 mass%) of the benzyl methacrylate / methacrylic acid copolymer (= 70/30 [mass ratio] copolymer, weight average molecular weight Mw: 8000)

ㆍ 77 parts of propylene glycol monomethyl ether acetate

(Comparative Example 6)

In Example 6, benzyl methacrylate / glycidyl methacrylate (unsaturated-basic acid adduct) / dicyclopentenyl methacrylate copolymer (acrylic copolymer according to the present invention) in the composition is benzyl methacryl A photocurable coloring composition was prepared and evaluated in the same manner as in Example 6 except that the rate / methacrylic acid copolymer = 70/30 [mass ratio] copolymer and the weight average molecular weight Mw: 8000) copolymer were changed. .

<Evaluation>

(Evaluation evaluation)

The photocurable coloring composition obtained in each Example and Comparative Example was cut to 100 mm x 100 mm of alkali-free glass 1737 of Corning Incorporated, 0.7 mm thick, and cleaned on a 1 mass% sodium hydroxide aqueous solution, using a spin coater. After baking, the substrate rotation speed was set so that BM might be 1.1 micrometer and RGB might be 2.0 micrometer, and it applied by the point dispensing method. Subsequently, heating (prebaking) was performed at 120 ° C. for 120 seconds using a hot plate, and then 100 mmJ / cm ² with a proximity gap of 300 μm using a mask having a line width of 15 μm using a HITACHI exposure machine LE4000A (full wavelength). Exposed to light (roughness: 20 mW / cm ² ). Thereafter, a grid pattern was formed by developing with 1.0% developer (25 ° C) of alkaline developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). At this time, the change of the line width with respect to the development time of a grating pattern was measured with the optical microscope (200 times). The measured value of the line width with respect to the developing time is shown in Table 1 below. From the measured values, the development margin and the development latitude are shown in the graphs shown in Figs. 1 to 4 as line width changes with respect to the development time.

Here, the development margin refers to the change in line width with respect to the development time, and the development latitude refers to the time from the expression of the pattern to the pattern peeling, that is, the length of the development time that can maintain the line width. That is, the smaller the value of the change in the line width with respect to the development time indicates that the development margin is superior in practical use, and the longer development time that can maintain the line width indicates that the development latitude is excellent.

(Developing profile)

The cross-sectional pattern profile at the developing time of 90 seconds obtained from the above developability evaluation results was observed by SEM (electron microscope) 5000 times). The angle with the board | substrate of the edge of a cross section was measured, and it described in Table 1 as a pattern angle.

In Table 1, "UC" means an undercut, and shows the state in which the board | substrate side is small in a surface layer part.

As shown in the graphs of Figs. 1 to 4, in the Examples, the line width is high, the sensitivity is high, the line width change with respect to the developing time is small, and the developing time for maintaining the line width is long, so that the developing margin and developing latitude are excellent. Moreover, as can be seen from Table 1, it was found that when the photocurable coloring composition of the present invention was used, even when a high pigment concentration was obtained, there was no occurrence of UC and a good developing pattern was exhibited.

According to the present invention, a photocurable coloring composition having a high sensitivity and maintaining a high sensitivity even with a high concentration of a coloring agent and having good developability of a developing margin and a developing latitude and a high optical density, sharp black matrix and high contrast It is possible to obtain colored pixels with high color purity, and to provide a high quality color filter and a liquid crystal display device using the same.

Claims (9)

In a photocurable coloring composition containing a colorant, an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator, the alkali-soluble resin is used in the side chain in an alkali-soluble group, a polymerizable double bond, and the following hydrophobic groups (a) and (b). It is an acrylic copolymer which has one or more, The photocurable coloring composition characterized by the above-mentioned.

Content of the said coloring agent is 30 mass% or more of the total mass of a nonvolatile component, The photocurable coloring composition of Claim 1 characterized by the above-mentioned.  The said colorant is black, and content of the said coloring agent is 47 mass% or more of the total mass of a nonvolatile component, The photocurable coloring composition of Claim 1 or 2 characterized by the above-mentioned.  The photocurable coloring composition according to claim 3, wherein the black colorant is at least one selected from carbon black, titanium black and graphite. The said colorant is red, and content of the said coloring agent is 30 mass% or more of the total mass of a nonvolatile component, The photocurable coloring composition of Claim 1 or 2 characterized by the above-mentioned. The said colorant is green, and content of the said coloring agent is 45 mass% or more of the total mass of a nonvolatile component, The photocurable coloring composition of Claim 1 or 2 characterized by the above-mentioned. The said colorant is blue, and content of the said coloring agent is 30 mass% or more of the total mass of a nonvolatile component, The photocurable coloring composition of Claim 1 or 2 characterized by the above-mentioned. The color filter formed using the photocurable coloring composition of any one of Claims 1-7. A liquid crystal display device comprising the color filter according to claim 8.

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