TWI813542B - Photosensitive coloring composition and color filter - Google Patents

Abstract

The present invention provides a photosensitive coloring composition that is highly sensitive even if the pigment content is high or the film is thick, and has excellent linearity and pattern shape, and a color filter using the same. , resolution, development resistance, chemical resistance, and can have excellent heat resistance. Provided is a photosensitive coloring composition containing a photopolymerization initiator (A) represented by general formula (1), a resin (B), a photopolymerizable compound (C), and a coloring agent (D). The photosensitive coloring composition may further contain a dispersant, and at least one selected from the group consisting of a resin (B), a colorant (D), and a dispersant may have an oxetanyl group.

Description

Photosensitive coloring compositions and color filters

The present invention relates to a photosensitive colored composition, and in particular to a liquid crystal display device using a white-emitting organic electroluminescence (EL) element (hereinafter sometimes referred to as an "organic EL element"). Among color filters used in color displays or solid-state imaging devices, high-sensitivity photosensitivity useful for forming red, green, blue, and other color filter segments and black matrices, etc. Coloring composition. Furthermore, white refers to a broad concept including pseudo-white color, and the present invention relates to a color filter formed using this photosensitive coloring composition.

Color filters include those in which two or more fine stripe-shaped filter segments of different hues are arranged in parallel or crosswise on the surface of a transparent substrate such as glass, or in which fine filters are The segments are arranged in a certain vertical and horizontal arrangement. The filter segments are as fine as several microns to hundreds of microns, and are neatly arranged in a prescribed arrangement according to the hue.

Generally speaking, in a color liquid crystal display device, a transparent electrode for driving the liquid crystal is formed on the color filter by evaporation or sputtering, and then a transparent electrode for driving the liquid crystal in a certain direction is formed thereon. Alignment film. To fully obtain the performance of these transparent electrodes and alignment films, their formation needs to be carried out at a high temperature generally above 200°C, preferably above 230°C.

Therefore, currently, the mainstream method for manufacturing color filters is a method called a pigment dispersion method, which uses a pigment with excellent light resistance and heat resistance as a coloring material.

In the case of the pigment dispersion method, a photosensitive coloring composition (pigment resist) in which a pigment is dispersed in a photosensitive resin solution is coated on a transparent substrate such as glass, and the solvent is removed by drying, followed by filtration. The pattern of the light filter color is exposed, and then the unexposed part is removed using a development step to form a pattern of the first color. After adding heating and other treatments as necessary, the same operation is repeated for all filter colors in sequence, thereby manufacturing Color filters.

In recent years, color liquid crystal display devices have formed a huge market as notebook personal computers for liquid crystal color televisions or car navigation systems that are integrated with a liquid crystal display device, and they also take advantage of energy-saving and space-saving features. Monitors and televisions for desktop personal computers began to spread. Although it has attracted attention as a display device replacing the existing cathode ray tube (CRT), the color reproduction characteristics of liquid crystal display devices are currently inferior to those of CRT.

Therefore, the requirement for high color reproducibility has increased in color filters in which filter segments of various colors are arranged.

In addition, in order to improve the contrast, a black matrix is generally placed between the filter segments of each color of the color filter. However, in recent years, regarding the material for forming the black matrix, environmental issues, low reflection, and cost reduction have been From the perspective of this, instead of metallic chromium black matrices, attention is paid to resin black matrices in which light-shielding pigments are dispersed in resin. Array. However, a resin black matrix has a problem of lower light-shielding properties (optical density) than a metal chromium black matrix.

In order to improve the color reproduction characteristics of the color filter and the light-shielding property of the black matrix, it is necessary to increase the pigment content in the photosensitive coloring composition or increase the film thickness. However, the method of increasing the pigment content causes problems such as a decrease in sensitivity, deterioration of developability, and resolution. In the method of increasing the film thickness, problems such as exposure light not reaching the bottom of the film and poor pattern shape arise.

In order to solve this problem, it is necessary to increase the sensitivity of the photosensitive coloring composition. Generally speaking, (1) providing reactive double bonds to the resin; (2) selecting or sensitizing the photopolymerization initiator and sensitizer. Amount; (3) Selection or increase of monomers, etc. Examples include Patent Document 1 and Patent Document 2.

[Prior art documents] [Patent Document]

Patent Document 1: Japanese Patent Application Publication No. 2001-264530

Patent Document 2: Japanese Patent Application Publication No. 2003-156842

However, there is a limit to sensitivity improvement simply by providing double bonds to the resin or selecting photopolymerization initiators, sensitizers, and monomers. In particular, if the amount of the photopolymerization initiator is increased, coloration due to a color unique to the photopolymerization initiator, a decrease in heat resistance, a decrease in light transmittance, a decrease in resolution, etc. occur. In addition, if the amount of monomer is increased, problems such as tack may occur.

Therefore, an object of embodiments of the present invention is to provide a device that is highly sensitive even if the pigment content is high or the film thickness is thick, and is excellent in linearity, pattern shape, resolution, development resistance, and chemical resistance, and can also be used A photosensitive colored composition having excellent heat resistance, and a color filter using the same.

The photosensitive colored composition according to one embodiment of the present invention is characterized by using the following general formula ( 1) Photopolymerization initiator represented.

That is, the photosensitive colored composition according to one embodiment of the present invention contains the photopolymerization initiator (A) represented by the following general formula (1) and contains a resin (B), a photopolymerizable compound (C), and a coloring Photosensitive coloring composition of agent (D).

The photosensitive colored composition according to another embodiment of the present invention is characterized in that in order to achieve high sensitivity and obtain excellent linearity, pattern shape, resolution, development resistance, chemical resistance, and heat resistance, the following is used: The photopolymerization initiator represented by the general formula (1), and at least one selected from the group consisting of resins, colorants, and dispersants has an oxetane group.

That is, the photosensitive colored composition according to one embodiment of the present invention is a photosensitive colored composition containing a photopolymerization initiator (A) represented by the following general formula (1) and a resin (B), a photopolymerizable The compound (C), the colorant (D) and the dispersing agent are selected from the group consisting of the resin (B), the coloring agent (D) and the dispersing agent, and at least one of them has an oxetanyl group.

[In the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkenyl group, Substituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclyl, substituted or unsubstituted heterocyclic oxy, substituted or unsubstituted alkylmercapto, substituted or unsubstituted arylmercapto, substituted or unsubstituted acyl, or substituted or unsubstituted Amino group. ]

In addition, one embodiment of the present invention relates to the photosensitive coloring composition, wherein the dispersant has an oxetane group, and the dispersant contains a dispersant (X), and the dispersant ( X) has: polyester part X1', which is selected from tetracarboxylic dianhydride (b1) and tricarboxylic anhydride (b2) The acid anhydride group in (b) is formed by reacting with the hydroxyl group in the hydroxyl-containing compound (a), and has a carboxyl group; and the vinyl polymer part X2', for the ethylenically unsaturated monomer ( c) It is formed by free radical polymerization, and part of X2' has an oxetanyl group.

Moreover, one embodiment of this invention is related with the said photosensitive coloring composition, It is characterized by further containing another photopolymerization initiator (Y).

In addition, one embodiment of the present invention relates to the photosensitive coloring composition, wherein the other photopolymerization initiator (Y) contains a compound selected from the group consisting of an acetophenone compound, a phosphine compound, and an imidazole compound. at least one compound from the group consisting of.

Moreover, one embodiment of this invention is related with the said photosensitive coloring composition, It is characterized by further containing a silane coupling agent (S).

Moreover, one embodiment of this invention is related with the said photosensitive coloring composition, It is characterized by further containing a polyfunctional thiol (F).

In addition, one embodiment of the present invention relates to a color filter, which is characterized in that a filter segment or a black matrix formed of the photosensitive coloring composition is provided on a transparent substrate.

The photosensitive coloring composition according to the embodiment of the present invention uses a specific oxime ester compound as a photopolymerization initiator, thereby forming a film with a high pigment content or a thick film of each color filter segment and black matrix. It is also highly sensitive and has excellent It has excellent linearity, pattern shape, resolution, development resistance, and chemical resistance, and can have various color filter segments and black matrix patterns with excellent heat resistance.

Therefore, by using the photosensitive coloring composition of the present invention, a high-quality color filter can be obtained.

First, the photosensitive coloring composition of the present invention will be described in detail.

The photosensitive colored composition according to one embodiment of the present invention contains the photopolymerization initiator (A) represented by the general formula (1), and contains a resin (B), a photopolymerizable compound (C), and a coloring agent (D).

A photosensitive colored composition according to another embodiment of the present invention contains a photopolymerization initiator (A) represented by the general formula (1), a resin (B), a photopolymerizable compound (C), and a colorant (D). and a dispersant, at least one selected from the group consisting of resin (B), colorant (D) and dispersant having an oxetanyl group.

The photopolymerization initiator (A) containing the compound represented by the general formula (1) has high sensitivity and can obtain a coating film with a high residual film ratio in particular. Therefore, it is possible to obtain photosensitivity with excellent production stability of a color filter. Coloring composition. By using a photosensitive colored composition containing this photopolymerization initiator, filter segments and black matrices excellent in linearity, pattern shape, resolution, development resistance, and chemical resistance can be formed.

In addition, by using other initiators together, a more favorable pattern shape can be obtained.

In addition, by using a resin selected from the group consisting of resin (B), colorant (D) and dispersant At least one of them has an oxetanyl group and has excellent heat resistance after curing. Therefore, by using a photosensitive coloring composition containing this structure, it is possible to form filter segments and black matrices with excellent heat resistance.

<Photopolymerization initiator (A)>

The photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention is a compound represented by general formula (1).

R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or Unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclyl, substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylmercapto group, a substituted or unsubstituted arylmercapto group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amine group.

The hydrogen atoms of the substituents in R ₁ to R ₄ may be further substituted by other substituents.

Examples of such substituents include: halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; phenoxy group and p-tolyloxy group Aryloxy groups such as (p-tolyloxy); alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acetyloxy, propyloxy, benzoyloxy and other acyloxy groups; Acetyl, benzyl, isobutyl, acryl, methacryl, methoxyl and other alkyl mercapto groups; methyl mercapto, tert-butyl mercapto and other alkyl mercapto groups; phenyl mercapto, p- Aryl mercapto groups such as tolyl mercapto group; alkylamino groups such as methylamino group and cyclohexylamino group; dimethylamino group, diethylamino group, morpholino group, piperidino group etc. Alkylamino; phenylamine, p-tolylamino and other arylamine groups; methyl, ethyl, tert-butyl, dodecyl and other alkyl groups; phenyl, p-tolyl, xylyl, Aryl groups such as cumyl, naphthyl, anthryl, phenanthrenyl, benzofuranyl, etc.; heterocyclic groups such as furyl, thienyl, etc. In addition, examples include: hydroxyl group, carboxyl group, formyl group, Mercapto, sulfo, methanesulfonyl, p-toluenesulfonyl, amine, nitro, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinico base, phosphonium group, trimethylammonium group, dimethylsonium group, triphenylbenzoylmethylphosphonium group, etc.

Examples of optimal structures of the photopolymerization initiator (A) include compounds represented by the following formula (2) and formula (3).

The photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention is an oxime ester-based photopolymerization initiator. It is believed that the oxime ester photopolymerization initiator partially decomposes the oxime ester by absorbing ultraviolet rays and generates imine radicals and alkoxy radicals. Further, The free radicals of the active species generated by decomposition cause the reaction, but the photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention has a structure represented by the general formula (1), which is caused by ultraviolet irradiation. The decomposition efficiency is very high and patterns can be formed with a small amount of exposure.

As a reason why the photopolymerization initiator (A) of the present invention can function with higher sensitivity than conventional initiators, the following two reasons are considered as possible, but the details are not clear.

The first reason is that the structure represented by the general formula (1) has good ultraviolet absorption performance, whereby the photopolymerization initiator (A) of the present invention can absorb the energy of the given energy ray extremely well. Furthermore, it is thought that the obtained energy is efficiently used for decomposition of the oxime ester site, whereby decomposition by energy ray irradiation is rapid and a large amount of free radicals can be generated instantaneously.

As a second reason, it is considered that the photopolymerization initiator (A) of the present invention decomposes imine radicals generated by absorbing ultraviolet rays into active species radicals due to the structure represented by the general formula (1), And very fast. If the generated imine radical is metastable, the decomposition will be slowed down and the production of active radicals will be reduced. This situation is greatly affected by the chemical structure of the ultraviolet absorbing part. It is considered that the photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1), and the imine radical generated due to decomposition by light irradiation decomposes very quickly, thereby generating a large amount of free radicals. base results.

In addition, as described above, regarding the photopolymerization initiator (A) of the present invention, it is considered that decomposition of imine radicals is very rapid, and therefore rebonding is suppressed. More bonding In this case, the number of active species generated by decomposition will decrease, so the function as a radical polymerization initiator will decrease.

The photopolymerization initiator (A) represented by the general formula (1) can be preferably 1 to 50 parts by weight, and particularly preferably 1 part by weight relative to 100 parts by weight of the colorant (D) in the photosensitive coloring composition. Use in an amount of ~30 parts by weight.

<Other photopolymerization initiators (Y)>

In the photosensitive coloring composition according to the embodiment of the present invention, a more favorable pattern shape can be obtained by using the photopolymerization initiator (A) represented by the general formula (1) in combination with another photopolymerization initiator (Y). Better.

As other photopolymerization initiators (Y), 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, and p-dimethylamine can be used Acetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1- Ketone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. Ketone compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl ester , 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4 '-Tetrakis(tert-butylperoxycarbonyl)benzophenone and other benzophenone compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, Thioxanthone compounds such as 2,4-diisopropylthioxanthone and 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6 -Bis(trichloromethyl)-tris Azine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine Triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalene -1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)- Triazines such as s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl(4'-methoxystyryl)-6-triazine Compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime), O-(acetyl)-N-(1 -Oxime ester compounds such as phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylene)hydroxyamine; bis(2,4,6-trimethylbenzyl) Phosphine compounds such as phenylphosphine oxide and 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide; 2,2'-bis(o-chlorophenyl)-4,5,4', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2' -Imidazole compounds such as bis(o-chlorophenyl)-4,4',5,5'-tetrakis(p-methylphenyl)biimidazole; quinones such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone series compounds; borate series compounds; carbazole series compounds; titanocene series compounds, etc.

Among these, it is more preferable to include at least one photopolymerization initiator (Y) selected from the group consisting of an acetophenone-based compound, a phosphine-based compound, and an imidazole-based compound.

These other photopolymerization initiators (Y) may be used alone, or two or more may be mixed and used at any ratio as necessary. The other photopolymerization initiator (Y) can be used in an amount of 1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the colorant (D) in the photosensitive coloring composition. .

In addition, it can be used in an amount of 1 to 3000 parts by weight relative to 100 parts by weight of the photopolymerization initiator (A). In order to obtain a better pattern shape, it is preferably 5 to 2000 parts by weight based on 100 parts by weight of the photopolymerization initiator (A). quantity.

<Sensitizer(E)>

Furthermore, the photosensitive coloring composition according to the embodiment of the present invention may contain a sensitizer (E). The content of the sensitizer (E) can be used in an amount of 1 to 200 parts by weight relative to 100 parts by weight of the photopolymerization initiator (A) in the photosensitive coloring composition.

Examples of the sensitizer (E) include: unsaturated ketones represented by chalcone derivatives or dibenzylidene acetone; 1,2-diketone derivatives represented by benzyl or camphorquinone; benzoin Derivatives, fluorine derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, coumarinone derivatives polymethine pigments, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine pigments; acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indole Phrin derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzo Porphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliroporphyrazine derivatives, naphthalocyanine ( naphthalocyanine derivatives, subphthalocyanine derivatives, pyranium derivatives, thiopyranium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazines Derivatives, thiospiropyran derivatives, metal aromatic hydrocarbon complexes, organic ruthenium complexes, Michlerone derivatives, etc.

Further specific examples include: "Handbook of Pigments" (1986, Kodansha) edited by Nobu Okawara et al., "Chemistry of Functional Pigments" (1981, CMC) edited by Nobu Okawara et al., Chuzaburo Ikemori et al. Sensitizers described in "Special Functional Materials" (1986, CMC), but are not limited to these. In addition, a sensitizer that exhibits absorption of light in the ultraviolet to near-infrared range may be included.

Among the sensitizers (E), examples of sensitizers that can particularly suitably sensitize the compound represented by the general formula (1) include thioxanthone derivatives, Michlerone derivatives, and carbazole derivatives. things. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone can be used Anthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone Ketone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoylcarbazole -N-ethylcarbazole, etc.

The sensitizer (E) may contain two or more sensitizers at any ratio.

<Resin(B)>

The resin (B) contained in the photosensitive colored composition according to the embodiment of the present invention has a transmittance of preferably 80% or more, more preferably 95% or more in the total wavelength range of 400 nm to 700 nm in the visible light region. The resin (B) includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these can be used alone or in combination of two or more.

Examples of thermoplastic resins include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride-ethyl acetate. Vinyl ester copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, Cellulose, polyethylene, polybutadiene, polyimide resin, etc.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, phenol resin, and the like.

As the photosensitive resin, a resin obtained by reacting a (meth)acrylic compound or cinnamic acid having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group with a hydroxyl group, a carboxyl group, an amine group, etc., can be used. It is obtained by reacting a linear polymer with a linear polymer having a linear substituent and introducing photo-crosslinkable groups such as (meth)acrylyl group and styrene group into the linear polymer. In addition, a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer can also be used using a (meth)acrylic acid compound having a hydroxyl group such as hydroxyalkyl (meth)acrylate. It is formed by the semi-esterification of linear polymers containing acid anhydrides.

The resin having an oxetanyl group can be realized, for example, by copolymerizing an ethylenically unsaturated monomer having an oxetanyl group.

Examples of the ethylenically unsaturated monomer having an oxetanyl group include (meth)acrylic acid (3-methyl-3-oxetanyl)methyl ester, (meth)acrylic acid (3-ethyl) -3-oxetanyl)methyl ester, (meth)acrylic acid (3-butyl-3-oxetanyl)methyl ester, (meth)acrylic acid (3-hexyl-3-oxetane) base) methyl ester, etc.

Examples of commercially available products include: ETERNACOLL, OXMA (manufactured by Mobe Kosan Co., Ltd.), OXE-10, OXE-30 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc.

Since the resin has an oxetane group, the colored composition containing the resin has excellent heat resistance after curing.

The resin (B) can be used in an amount of 1 to 400 parts by weight, preferably 1 to 300 parts by weight, based on 100 parts by weight of the colorant (D) in the photosensitive coloring composition.

<Photopolymerizable compound (C)>

The photopolymerizable compound (C) contained in the photosensitive coloring composition according to the embodiment of the present invention is a photopolymerizable monomer or oligomer, and examples thereof include (meth)methyl acrylate and ethyl (meth)acrylate. Ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di( Meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate Meth)acrylate, pentaerythritol tri(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, new Pentylene glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tricyclodecyl (meth)acrylate, ester acrylate, hydroxymethylated melamine (meth) Various acrylates and methacrylates such as acrylate, epoxy (meth)acrylate, acrylic urethane, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol Alcohol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-ethylene Methanamide, acrylonitrile, etc. These can be used individually or in mixture of 2 or more types.

The photopolymerizable compound (C) can be used in an amount of 5 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the colorant (D) in the photosensitive coloring composition.

In the photosensitive coloring composition, the ratio [I _a /M] of the weight [I _a ] of the photopolymerization initiator (A) to the weight [M] of the photopolymerizable compound (C) is preferably 0.01 to 3.00. More preferably, it is 0.15~2.00.

Furthermore, when the photosensitive coloring composition contains a sensitizer (E) or other photopolymerization initiator (Y), the photopolymerization initiator (A), sensitizer (E) and other photopolymerization initiators The ratio [I _b /M] of the total weight (I _b ) of the agent (Y) and the weight [M] of the photopolymerizable compound (C) is preferably 0.01 to 3.00, more preferably 0.15 to 2.00.

When [I _a /M] is 0.15 or more, the development resistance is good, and when [I _b /M] is 0.15 or more, the chemical resistance is also good. In addition, when [I _a /M] is 2.00 or less and [I _b /M] is 2.00 or less, the pattern shape, linearity, and resolution are more excellent.

<Color(D)>

As the colorant (D) contained in the photosensitive coloring composition according to the embodiment of the present invention, an organic pigment or an inorganic pigment can be used alone, or two or more types can be mixed and used. Among pigments, those with high color development and high heat resistance are preferred, and organic pigments are usually used. Hereinafter, specific examples of organic pigments that can be used in the photosensitive coloring composition according to the embodiment of the present invention are represented by color index numbers.

In addition, the colorant (D) may contain a dye within a range that does not reduce heat resistance.

The coloring agent having an oxetanyl group can, for example, be composed of a dye containing This is achieved by using an ethylenically unsaturated monomer containing an oxetane structure in the resin of the salt-forming compound of the material. By having an oxetanyl group, the coloring composition containing this coloring agent has excellent heat resistance after curing.

Examples of red pigments include: Color Index (C.I.) Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. Among these, from the viewpoint of brightness and coloring power, azo pigments, diketopyrrolopyrrole series, anthraquinone series, quinophthalone series, isoindoline series, ioconone series, perylene series and benzimidazolone-based pigments. Specifically, C.I. Pigment Red 176, 177, 179, 254, 242 and a naphthol azo pigment represented by the following general formula (4) are preferred.

General formula (4) [Chemical formula 5]

[In the general formula (4), A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ or -COOR ⁸ . R ² to R ⁶ independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁹ , -COOR ¹⁰ , -CONHR ¹¹ , -NHCOR ¹² or -SO ₂ NHR ¹³ . R ⁷ to R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Among them, R ⁴ is -NHCOR ¹² , A, R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms, except when R ¹ is a halogen atom. ]

Examples of blue pigments include: C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 etc. Among these, from the viewpoint of brightness and coloring power, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 or 15:6 is preferred, and C.I. Pigment Blue 15: is more preferred. 6. In addition, you can also use Japanese Patent Application 2004-333817, Japanese Patent No. 4893859, etc., but are not particularly limited to these.

Examples of green pigments include: C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 ,59,62,63. Among these, from the viewpoint of brightness and tinting power, C.I. Pigment Green 7, 36, 58, 59, 62, and 63 are preferred. In addition, zinc phthalocyanine pigments, etc. described in Japanese Patent Laid-Open No. 2008-19383, Japanese Patent Laid-Open No. 2007-320986, Japanese Patent Laid-Open No. 2004-70342, etc. can also be used, and are not particularly limited to these. some.

Examples of yellow pigments include: C.I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35 : 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83 , 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134 ,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170 , 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199 , 200, 202, 203, 204, 205, 206, 207, 208, 231, etc. Among these, from the viewpoint of brightness and tinting power, C.I. Pigment Yellow 138, 139, 150, 185, and 231 are preferred. In addition, quinophthalone-based pigments described in Japanese Patent No. 4993026 may also be used, and no special Don't limit yourself to these.

Examples of purple pigments include: C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27 , 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Among these, from the viewpoint of brightness and coloring power, C.I. Pigment Violet 19 or 23 is preferred, and C.I. Pigment Violet 23 is more preferred.

Examples of orange pigments include C.I. Pigment Orange 38, 43, 64, 71 or 73. Among them, from the viewpoint of brightness and tinting power, C.I. Pigment Orange 38, 43 and 64 are preferred.

For the black photosensitive coloring composition used to form the black matrix, for example, carbon black, aniline black, anthraquinone-based black pigments, and perylene-based black pigments can be used. Specifically, C.I. Pigment Black 1, 6, 7, 12, 20, 31, etc. A mixture of red pigments, blue pigments, and green pigments can also be used in the black photosensitive coloring composition. As the black pigment, carbon black is preferred in terms of price and light-shielding properties. Carbon black can also be surface-treated with resin or the like. In addition, in order to adjust the color tone, a blue pigment or a purple pigment may be used together with the black photosensitive coloring composition.

Examples of inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, iron lead (red iron (III) oxide), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, and amber. , titanium black, synthetic iron black, titanium oxide, iron tetroxide and other metal oxide powders, metal sulfide powders, metal powders, etc. In order to achieve a balance between chroma and brightness and ensure good coating properties, sensitivity, developability, etc., inorganic pigments can be used in combination with organic pigments.

"dye"

The colored composition according to the embodiment of the present invention can use a dye as a colorant. As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. can be used. In addition, these derivatives or the form of a lake pigment obtained by lake-forming a dye may also be used.

Furthermore, in the case of an acid dye or a direct dye having an acidic group such as sulfonic acid or carboxylic acid, it can be produced by using an inorganic salt used as an acid dye or an acid dye and a quaternary ammonium salt compound or a tertiary amine compound. A secondary amine compound or a salt-forming compound of a nitrogen-containing compound such as a primary amine compound may be salified using a resin component having such a functional group and used as a salt-forming compound, or a sulfonyl amination may be performed and used as a sulfonyl compound. The amine compound has excellent resistance, so it can be made into a colored composition with excellent fastness, which is preferable.

In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferable because of its excellent fastness. More preferably, the compound having an onium salt group is a resin having a cationic group in a side chain.

When it is in the form of a basic dye, it can be salified using an organic acid, perchloric acid, or a metal salt thereof. It is preferable to use a salt-forming compound of a basic dye because it has excellent resistance to use with pigments. It is even more preferable to use a salt-forming compound that acts as a counter ion for a basic dye. The counteractive components are organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus anion compound, fluorine group-containing boron anion compound, cyano group-containing nitrogen anion compound, and anion containing the conjugate base of an organic acid having a halogenated hydrocarbon group. compound, or acidic The dye is obtained by salt formation.

In addition, it is preferable to have a polymerizable unsaturated group in the dye skeleton because a dye with excellent resistance can be produced.

In addition, when the dye has an oxetanyl group, the colored composition containing the dye has excellent heat resistance after curing.

In one embodiment, the chemical structure of the dye includes, for example, a pigment structure derived from a dye selected from the group consisting of azo dyes, azomethine dyes (indigoaniline dyes, indophenol dyes, etc.), Dipyrrromethylene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenyl dyes, etc.) Methane-based dyes, xanthene-based dyes, acridine-based dyes, etc.), quinoneimine-based dyes (oxazine-based dyes, thiazine-based dyes, etc.), azine-based dyes, polymethine-based dyes (oxocyanine-based dyes, etc.) Dyes, merocyanine-based dyes, arylene-based dyes, styrene-based dyes, cyanine-based dyes, squaraine-based dyes, ketonium-based dyes, etc.), quinophthalone-based dyes, phthalocyanine-based dyes, Subphthalocyanine dyes, ionone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and metal complex dyes thereof, etc.

Among these pigment structures, from the viewpoint of color characteristics such as hue, color separability, and color unevenness, a pigment structure derived from a pigment selected from the group consisting of azo dyes, xanthene dyes, and floral dyes is preferred. Cyan-based dyes, triphenylmethane-based dyes, anthraquinone-based dyes, dipyrromethane-based dyes, squaraine-based dyes, quinophthalone-based dyes, phthalocyanine-based dyes, sub-phthalocyanine-based dyes, more preferably Pigment structure derived from the following pigments selected from the group consisting of xanthene dyes, cyanine dyes, triphenylmethane dyes, Anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes. Regarding specific pigment compounds that can form pigment structures, see "New Edition of Dyes Handbook" (compiled by the Society of Organic Synthetic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), and "Handbook of Pigments" ” (edited by Nobu Ogawara and others; Kodansha, 1986) etc.

Examples of dyes in another embodiment include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, methine dyes, and dimethicone dyes. Arylmethane dyes, triarylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, oxazine dyes , Perylene dyes, diketopyrrolopyrrole dyes, quinacridone dyes, anthraquinone (anthanthrone) dyes, isoindolinone dyes, isoindoline dyes, indanthrone dyes Dyes, coumarin-based dyes, pyranthrone-based dyes, flavanthrone-based dyes, flavanthrone-based dyes, etc., but are not limited to these.

In yet another embodiment, organic dyes that can be used include triarylmethane-based dyes, xanthene-based dyes, and anthraquinone-based dyes. Among them, xanthene-based dyes are preferably used.

[Xanthene dyes]

The xanthene-based dyes that can be preferably used are dyes that exhibit red or purple colors, and are preferably in the form of any one of oil-soluble dyes, acid dyes, direct dyes, and basic dyes. Alternatively, the dyes may be in the form of lake pigments obtained by lake-forming these dyes.

Among these, xanthene-based oil-soluble dyes and xanthene-based acid dyes are preferably used because they have excellent hues.

Dyes that exhibit red and purple include the following dyes: oil-soluble dyes such as C.I. solvent red and C.I. solvent violet; basic dyes such as C.I. basic red and C.I. basic violet; acidic dyes such as C.I. acid red and C.I. acid violet Dyes; C.I. direct red, C.I. direct violet and other direct dyes, etc.

Here, the direct dye has a sulfonic acid group (-SO ₃ H, -SO ₃ Na) in the structure. In this disclosure, the direct dye is regarded as an acid dye.

In addition, the xanthene-based basic dye is preferably used by salting it using an organic acid or perchloric acid. As the organic acid, organic sulfonic acid and organic carboxylic acid are preferably used. Among them, in terms of resistance, it is preferable to use naphthalene sulfonic acid such as tobias acid and perchloric acid.

In addition, in terms of durability, xanthene-based acid dyes are preferably produced using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., or resin components having these functional groups. It is salified and used as a salt-forming compound, or it is sulfonamided and used as a sulfonamide compound.

Salt-forming compounds of xanthene-based acid dyes and/or sulfonamide compounds of xanthene-based acid dyes are preferred because of their excellent hue and resistance, and it is further more preferred to use compounds that act as counterions to the xanthene-based acid dyes. The counter components are a compound obtained by salifying a quaternary ammonium salt compound and a sulfonamide compound obtained by sulfonamidating a xanthene-based acid dye.

In addition, among the xanthene-based dyes, rhodamine-based dyes are preferred because of their excellent color development properties and tolerance.

Hereinafter, the form of the xanthene-based pigment will be described in detail.

[Xanthene-based oil-soluble dyes]

Examples of xanthene oil-soluble dyes include: C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 42, C.I. Solvent Red 43, C.I. Solvent Red 44, C.I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, C.I. Solvent Red 109, C.I. Solvent Red 140, C.I. Solvent Red 141, C.I. Solvent Red 237, C.I. Solvent Red 246, C.I. Solvent Violet 2, C.I. Solvent violet 10 etc.

Among them, C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 49, C.I. Solvent Red 109, C.I. Solvent Red 237, C.I. Solvent Red 246, C.I. Solvent Violet 2.

[Xanthene-based basic dyes]

Examples of xanthene-based basic dyes include: C.I. Basic Red 1 (Rhodamine 6GCP), 8 (Rhodamine G), C.I. Basic Violet 10 (Rhodamine B), etc. Among them, C.I. Basic Red 1 and C.I. Basic Violet 10 are preferred in terms of excellent color rendering properties.

[Xanthene acid dye]

It is preferable to use the xanthene acid dyes C.I. Acid Red 51 (erythrophylla red (Food Red No. 3)), C.I. Acid Red 52 (Acid Rhodamine), C.I. Acid Red 87 (Eosin G (Food Red No. 103)) ), C.I. Acid Red 92 (Acid Phloxine PB (Food Red No. 104)), C.I. Acid Red 289, C.I. Acid Red 388, Rose Bengal B (Food Red No. 5), Acid If Danming G, C.I. Acid violet 9.

Among them, in terms of heat resistance and light resistance, it is more preferable to use xanthene C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 388, which are acid dyes, or C.I. Acid Red 52 (acid rhodamine), C.I. Acid Red 289, Acid Rhodamine G, which are rhodamine-based acid dyes. C.I. Acid Violet 9.

Among them, it is most preferable to use C.I. Acid Red 52 and C.I. Acid Red 289, which are rhodamine-based acid dyes, particularly in terms of excellent color development, heat resistance, and light resistance.

Acid dyes (not limited to xanthene series) are preferably salt-forming compounds of acid dyes and nitrogen-containing compounds, using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., or compounds having these It is preferable that the resin component of the functional group is salted to form a salt-forming compound of the acid dye, thereby imparting high heat resistance, light resistance, and solvent resistance. Acid dyes can also be given high heat resistance, light resistance, and solvent resistance through sulfonamide.

In addition, a salt-forming compound of an acidic dye and a compound having an onium salt group may also be used. Among them, the compound having an onium salt group is a resin having a cationic group in the side chain. This can produce a coloring composition with excellent brightness and durability. things.

Primary amine compounds include: methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, Undecylamine, dodecylamine (laurylamine), trilaurylamine, tetradecylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, Aliphatic unsaturated primary amines such as coconut oil alkylamine, tallow alkylamine, hardened tallow alkylamine, allylamine, aniline, benzylamine, etc.

Examples of secondary amine compounds include: dimethylamine, diethylamine, dipropylamine, Aliphatic unsaturated secondary amines such as diisopropylamine, dibutylamine, dipylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoane amine, dishardened tallow alkyl amine, distearyl amine, etc.

Examples of tertiary amine compounds include trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylaniline, diethylaniline, and tribenzylamine.

(quaternary ammonium salt compound)

When the organic dye used in the embodiment of the present invention is an acid dye, it is preferably used as the salt-forming compound (a) containing an acid dye and a quaternary ammonium salt compound.

The quaternary ammonium salt compound which is a counter component of an acid dye is demonstrated. Quaternary ammonium compounds become counterbalances to acid dyes by possessing amine groups.

A preferred form of the quaternary ammonium salt compound as a counter component of the salt-forming compound (a) is colorless or white. Here, colorless or white refers to a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more, in the total wavelength range of 400 nm to 700 nm in the visible light region. That is, those which do not hinder the color development of the dye component and which do not cause a color change are preferable.

The molecular weight of the counter portion of the cationic component of the quaternary ammonium salt compound is preferably in the range of 190 to 900. The cation part here corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) ⁺ part in the following general formula (3). If the molecular weight is less than 190, the light resistance and heat resistance will be reduced, and the solubility in the solvent may be reduced. In addition, if the molecular weight is greater than 900, the proportion of color-developing components in the molecule will decrease, the color rendering property will decrease, and the brightness may also decrease. More preferably, the molecular weight of the counter part is in the range of 240 to 850. Particularly preferably, the molecular weight of the counter part is in the range of 350 to 800. The molecular weight here is calculated based on the structural formula, and the atomic weight of C is set to 12, the atomic weight of H is set to 1, and the atomic weight of N is set to 14.

As the quaternary ammonium salt compound, a compound represented by the following general formula (3) can be used.

(In the general formula (5), R ₁ to R ₄ each independently represent an alkyl group or benzyl group having 1 to 20 carbon atoms, and the number of at least two or more Cs in R ₁ , R ₂ , R ₃ , and R ₄ is 5~20. Y ^- represents inorganic anion or organic anion.)

By setting the number of at least two C's in R ₁ to R ₄ to 5 to 20, the solubility in the solvent becomes good. If the alkyl group with the number of C's less than 5 is 3 or more, the solubility in the solvent becomes poor and foreign matter in the coating film is likely to be generated. In addition, if there is an alkyl group with the number of C exceeding 20, the color development property of the salt-forming compound (a) will be impaired.

The Y ^- component constituting the anion may be an inorganic anion or an organic anion, and is preferably a halogen, usually chlorine.

Quaternary ammonium salt compounds can be listed: tetramethylammonium chloride, tetraethylammonium chloride, monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, tristearylmonomethyl ammonium chloride ammonium chloride, cetyltrimethylammonium chloride, trioctyltrimethylammonium chloride, dioctyldimethylammonium chloride, monolauryltrimethylammonium chloride, dilauryldimethylammonium chloride Ammonium chloride, trilauryl benzyl ammonium chloride, tripentyl benzyl ammonium chloride, trihexyl benzyl ammonium chloride, trioctyl benzyl ammonium chloride, trilauryl benzyl ammonium chloride, benzyl ammonium chloride Dimethylstearylammonium chloride, benzyldimethyloctylammonium chloride, dialkyl (alkyl group is C14~C18) dimethylammonium chloride (hardened tallow), etc.

Specific examples of quaternary ammonium salt compound products include: Quartamin 24P, Quartamin 86P concentrated (conc.), Quartamin 60W, Quartamin (manufactured by Kao Corporation) Quartamin) 86W, Quartamin D86P, Sanisol C, Sanisol B-50, etc.; Arquad 210-80E, 2C manufactured by Lion Company -75, 2HT-75, 2HT flake, 2O-75I, 2HP-75, 2HP flake, etc., among which quartamin D86P (distearyl dimethyl ammonium chloride) , Arquad 2HT-75 (dialkyl (alkyl group is C14~C18) dimethyl ammonium chloride).

(Resin having a cationic group in the side chain)

When the organic dye used in the embodiment of the present invention is an acid dye, it is also preferably used as a salt-forming compound (a′) containing an acid dye and a resin having a cationic group in a side chain. For those used in obtaining the embodiments of the present invention A resin having a cationic group in the side chain of the salt-forming compound (a') will be described.

The resin having a cationic group in the side chain used to obtain the salt-forming compound is not particularly limited as long as it has at least one onium salt group in the side chain. However, from the viewpoint of availability, etc., a suitable onium salt structure is relatively Preferred are ammonium salts, phosphonium salts, sulfonium salts, diazonium salts and phosphonium salts. Taking storage stability (thermal stability) into consideration, ammonium salts, phosphonium salts and sulfonium salts are more preferred. More preferably, ammonium salts are used.

When preparing a blue coloring composition for color filters containing a salt-forming compound (a') and making it exhibit characteristics as a color filter, it is preferable to use and constitute a blue coloring composition for color filters. The binder resin of the colored composition is the same type of resin. In one embodiment of the present invention, an acrylic resin is preferably used as a binder resin in the coloring composition for color filters, so as to obtain the salt-forming compound (a') having a cationic group in the side chain. The resin is preferably an acrylic resin.

As a resin having a cationic group in a side chain, an alkali resin containing a structural unit represented by the following general formula (5) can be used. The cationic group in the general formula (5) forms a salt with the anionic group of the xanthene-based acid dye, whereby a salt-forming compound can be obtained.

General formula (5) [Chemical formula 7]

[In general formula (5), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁵² to R ⁵⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and two of R ⁵² to R ⁵⁴ may be bonded to each other to form a ring. . Q represents an alkylene group, an aryl group, -CONH-R ⁵⁵ -, -COO-R ⁵⁵ -, and R ⁵⁵ represents an alkylene group. Y ^- represents an inorganic anion or an organic anion. ]

Examples of the alkyl group in R ⁵¹ include methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-hexyl, and cyclohexyl. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

When the alkyl group represented by R ⁵¹ has a substituent, examples of the substituent include a hydroxyl group, an alkoxy group, and the like.

Among the above, R ⁵¹ is preferably a hydrogen atom or a methyl group.

In the general formula (5), R ⁵² to R ⁵⁴ may each independently include a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.

Here, examples of the alkyl group in R ⁵² to R ⁵⁴ include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl). base, n-tetradecyl, n-hexadecyl and n-octadecyl, etc.), branched alkyl (isopropyl, isobutyl, second butyl, third butyl, isopentyl, neopentyl, third tripentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl, etc.), cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and Cross-linked cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of the alkenyl group in R ⁵² to R ⁵⁴ include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc.), cycloalkene base (2-cyclohexenyl and 3-cyclohexenyl, etc.). The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms.

Examples of the aryl group in R ⁵² to R ⁵⁴ include monocyclic aryl groups (phenyl, etc.), condensed polycyclic aryl groups (naphthyl, anthracenyl, phenanthrenyl, anthraquinone, fluorenyl and naphthoquinone). etc.) and aromatic heterocyclic hydrocarbon groups (thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine) group), 9-oxoxanthanyl (a group derived from xanthone) and 9-oxoxanthanthyl (a group derived from thioxanthone), etc.).

When the alkyl group, alkenyl group, or aryl group represented by R ⁵² to R ⁵⁴ has a substituent, the substituent may be selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkenyl group, and a carboxyl group. , substituents in alkoxycarbonyl, carboxyl, phenyl, etc. Among these, the substituent is particularly preferably a halogen atom, a hydroxyl group, an alkoxy group, or a phenyl group.

From the viewpoint of stability, R ⁵² to R ⁵⁴ are preferably an optionally substituted alkyl group, and more preferably an unsubstituted alkyl group.

In addition, two of R ⁵² to R ⁵⁴ may be bonded to each other to form a ring.

In the general formula (5), the Q component connecting the vinyl moiety and the ammonium salt group represents an alkylene group, an aryl group, -CONH-R ⁵⁵ -, -COO-R ⁵⁵ -, and R ⁵⁵ represents an alkylene group, Among them, -CONH-R ⁵⁵ - and -COO-R ⁵⁵ - are preferred from the viewpoint of polymerizability and accessibility. In addition, R ⁵⁵ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The Y ^- component in the general formula (5) constituting the counter anion of the resin may be an inorganic anion or an organic anion. The counter anion can be any known one without limitation, and specific examples include: hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; and carbonic acid ions. ion, bicarbonate ion, nitrate ion, sulfate ion, sulfite ion, chromate ion, nickelchromate ion, phosphate ion, cyanide ion, permanganate ion, and further examples include ferric hexacyanoferric ( III) Complex ions such as acid ions, etc. From the viewpoint of synthesis adaptability or stability, halogen ions and carboxylate ions are preferred, and halogen ions are most preferred. When the counter anion is an organic acid ion such as carboxylate ion, the organic acid ion can be covalently bonded in the resin to form an intramolecular salt.

One method of introducing an oxetane group into a resin having a cationic group in a side chain is to combine an ethylenically unsaturated monomer containing an oxetane structure with a cation corresponding to the general formula (5) A method of copolymerizing ethylenically unsaturated monomers with vinyl groups.

Examples of ethylenically unsaturated monomers having an oxetanyl group include: (methyl)propyl (3-Methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, (3-butylmeth)acrylate (3-Hexyl-3-oxetanyl) methyl ester, (meth)acrylic acid (3-hexyl-3-oxetanyl) methyl ester, etc.

Examples of commercially available products include ETERNACOLL OXMA (manufactured by Ube Kosan Co., Ltd.), OXE-10, OXE-30 (the above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

(salt formation)

The salt-forming compound of an acid dye and a nitrogen-containing compound or a resin having a cationic group in a side chain can be produced by a conventionally known method. Specific techniques are disclosed in Japanese Patent Application Laid-Open No. 11-72969 and the like.

If a xanthene-based acid dye is used as an example, it is sufficient to dissolve the xanthene-based acid dye in water and then perform a salification treatment while adding and stirring a quaternary ammonium salt compound. Here, the sulfonic acid group (-SO ₃ H) and sodium sulfonate group (-SO ₃ Na) in the xanthene-based acid dye can be obtained by bonding with the ammonium group (NH ₄ ⁺ ) part of the quaternary ammonium salt compound. salt-forming compounds. In addition, instead of water, methanol and ethanol are also solvents that can be used during salification.

In addition, the salt-forming compound can be easily obtained by stirring or vibrating an aqueous solution in which a resin having a cationic group in a side chain represented by general formula (5) and an acid dye are dissolved, or by passing The aqueous solution of the resin having a cationic group in the side chain represented by the formula (5) and the aqueous solution of the acid dye are mixed with stirring or vibration. In an aqueous solution, the ammonium groups of the resin and the anionic groups of the acid dye are ionized, and these groups undergo ionic bonding, and the ionic bonding part becomes water-insoluble. And precipitate. On the contrary, the salt containing the counter anion of the resin and the counter cation of the acid dye is water-soluble and can be removed by washing with water or the like. Only one type of resin and acid dye having a cationic group in the side chain may be used, or multiple types having different structures may be used.

In addition, among other acidic dyes, a salt-forming compound with a nitrogen-containing compound or a resin having a cationic group in the side chain can be obtained using the same method as the xanthene-based dye.

(Sulfonamide compound)

The acid dye may be a sulfonamide compound obtained by reacting a sulfonamide compound with an anionic dye.

The sulfonamide compound of acid dyes that can be preferably used among acid dyes can be chlorinated by a common method to acid dyes having -SO ₃ H and -SO ₃ Na, so that -SO ₃ H becomes -SO ₂ Cl, and It is produced by reacting this compound with an amine having a -NH ₂ group.

In addition, as the amine compound that can be preferably used in sulfonamide amination, specifically, 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3-( 2-ethylhexyloxy)propylamine, 3-ethoxypropylamine, cyclohexylamine, etc.

If a xanthene-based acid dye is used as an example, when a sulfonamide compound obtained by modifying C.I. acid red 289 using 3-(2-ethylhexyloxy)propylamine is obtained, the C.I. acidic dye After the Red 289 sulfonamide is chlorinated, it reacts with a theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane to obtain the sulfonamide compound of C.I. Acid Red 289.

In addition, C.I. acid red was obtained using 3-(2-ethylhexyloxy)propylamine. In the case of sulfonamide compounds modified by 52, it is also necessary to chloride C.I. Acid Red 52 sulfonamide and then add the theoretical equivalent of 3-(2-ethylhexyloxy)propylamine in dioxane. It is sufficient to react to obtain a sulfonamide compound of C.I. Acid Red 52.

In addition, among other acid dyes, the same method as xanthene dyes can be used to obtain sulfonamide compounds.

Xanthene-based dyes can be used in Japanese Patent Application Publication No. 2010-032999, Japanese Patent Application Publication No. 2011-138094, Japanese Patent Application Publication No. 2011-227313, Japanese Patent Application Publication No. 2011-242752, and Japanese Patent Application Publication No. 2011-242752. Publication No. 2012-107192, Japanese Patent Application Publication No. 2013-033194, Japanese Patent Application Publication No. 2011-71888, Japanese Patent Application Publication No. 2013-72263, Japanese Patent Application Publication No. 2013-81209, Japanese Patent Application Publication No. 2013-81209, Japanese Patent Application Publication No. Publication No. 2014-173064, Japanese Patent Application Publication No. 2013-53028, Japanese Patent Application Publication No. 2013-52186, Japanese Patent Application Publication No. 2014-196392, Japanese Patent Application Publication No. 2014-196393, Japanese Patent Application Publication No. 2014-196393, Japanese Patent Application Publication No. Publication No. 2014-201714, Japanese Patent Publication No. 2014-201715, Japanese Patent Publication No. 2013-050693, Japanese Patent Publication No. 2013-178478, Japanese Patent Publication No. 2013-203956, International Publication No. 2013 /011687 pamphlet (pamphlet) and other well-known technology described.

In one embodiment, the xanthene dye is preferably C.I. Acid Red 51, C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, C.I. Acid Red 388, Rose Bengal B, Acid Red Rhodamine G, C.I. Acid Violet 9, C.I. Acid Violet 30. Among them, it is more preferable to use C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, C.I. Acid Red 388.

[Dipyrromethene dye]

The dipyrromethene dye is a dye having a partial structure derived from a dipyrromethene pigment as a pigment moiety, and is preferably a dipyrromethene compound, and a dipyrromethene compound derived from a metal or The dipyrromethene metal complex compound obtained from the metal compound is preferably a metal complex compound in which a structure represented by the general formula (6) is coordinated to a metal atom or a metal compound (hereinafter, appropriately referred to as "Dipyrromethene metal complex compound").

(Dipyrromethene metal complex compound)

A metal complex compound (dipyrromethene metal complex compound) in which a structure represented by the general formula (6) is coordinated to a metal atom or a metal compound will be described.

In the general formula (6), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.

The metal or metal compound may be any metal atom or metal compound that can form a complex, and includes a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. Metals or metal compounds include, for example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl ₃ , InCl ₃ , FeCl ₃ , TiCl ₂ , SnCl ₂ , SiCl ₂ , GeCl ₂ and other metal chlorides, TiO, VO and other metal oxides, Si(OH) ₂ and other metal hydroxides.

Among these, the metal or metal compound is preferably Fe, Zn, Mg, Si, Pt, Pd, Mo, or Mn from the viewpoint of stability, spectral characteristics, heat resistance, light resistance, and manufacturing adaptability of the complex. , Cu, Ni, Co, TiO, B or VO, more preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO, most preferably Fe, Zn, Cu, Co, B or VO.

As such a dipyrromethene-based dye, Japanese Patent Application Publication No. 2008-292970, Japanese Patent Application Publication No. 2010-85758, Japanese Patent Application Publication No. 2010-84009, and Japanese Patent Application Publication No. 2010-43530 can be used. , well-known technologies described in Japanese Patent Laid-Open No. 2013-080010, Japanese Patent Laid-Open No. 2013-210596, International Publication No. 2013/141156, etc.

[Triphenylmethane pigment]

Examples of the triphenylmethane dye skeleton include a diaminotriphenylmethane dye skeleton, a triaminotriphenylmethane dye skeleton, a rose acid dye skeleton having an OH group, and the like.

A triaminotriphenylmethane dye skeleton is preferred in terms of excellent color tone and excellent light fastness compared to other dye skeletons. Among them, a diphenylnaphthylmethane dye skeleton which is a basic dye is particularly preferred.

[Triphenylmethane-based basic dye]

Triphenylmethane-based basic dyes develop color by oxidizing the NH ₂ or OH group in the para position with respect to the central carbon to form a quinone structure.

It is divided into the following three types according to the number of NH ₂ and OH groups. Among them, the triaminoarylmethane-based basic dye is preferred in terms of emitting good blue, red, and green colors.

a) Diaminotriphenylmethane basic dye

b)Triaminotriphenylmethane basic dye

c) Rose red acid basic dye with OH group

Triaminotriphenylmethane-based basic dyes and diaminotriphenylmethane-based basic dyes are preferred because they have bright color tones and are superior to other basic dyes in sunlight fastness.

Blue-based triphenylmethane-based basic dyes have spectral characteristics that maintain high transmittance at 400nm~440nm, so they can be set to high brightness when used especially for forming blue filter segments. Therefore it is better.

Specific examples of triphenylmethane-based basic dyes include: C.I. basic violet 1 (methyl violet), C.I. basic violet 3 (crystal violet), C.I. basic violet 14 (magenta), C.I. alkali Basic Blue 1 (Basic Cyanine 6G), C.I. Basic Blue 5 (Basic Cyanine EX), C.I. Basic Blue 7 (Victoria Pure Blue BO), C.I. Basic Blue 26 (Victoria Blue B Concentrated (conc.) ), C.I. Basic Green 1 (Bright Green GX), C.I. Basic Green 4 (malachite green) etc.

Among them, in terms of brightness, it is preferable to use C.I. Basic Blue 7.

In the case of a triphenyl-based basic dye, it can be used by salifying it using an organic acid, perchloric acid or a metal salt thereof. Among them, salt-forming compounds of basic dyes are preferred because of their excellent resistance to use with pigments. More preferably, salt-forming compounds that act as counter ions against basic dyes are used. The counter component is an organic sulfonic acid, an organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound containing a conjugate base of an organic acid having a halogenated hydrocarbon group, or Acid dyes are obtained by forming salts.

Specifically, they are organic sulfonic acids such as heteropoly acids, aliphatic sulfonic acids, aromatic sulfonic acids, etc.; organic sulfuric acids such as aliphatic sulfuric acid, aromatic sulfuric acid, etc.; organic acids such as aromatic carboxylic acids, fatty acids and other organic carboxylic acids, Or those in the form of acid dyes. Alternatively, these metal salts may be used. In addition, a salt-forming compound with a resin having an acid group is also preferred.

(salt formation)

The salt-forming compounds of these basic dyes and anionic counterbalancers can be synthesized by conventionally known methods. Specific techniques are disclosed in Japanese Patent Application Laid-Open No. 2003-215850 and the like.

To give an example, it is sufficient to dissolve a triarylmethane-based basic dye in water and then perform a salification treatment while adding and stirring an organic sulfonic acid or (sodium organic sulfonate) solution. Here, a salt-forming compound in which the amine group (-NHC ₂ H ₅ ) part of the triarylmethane-based basic dye and the sulfonic acid group (-SO ₃ H) part of the organic sulfonic acid are bonded is obtained.

Here, the organic sulfonic acid may be dissolved in an alkaline solution such as sodium hydroxide and used in the form of sodium sulfonate (-SO ₃ Na) before the salt-forming treatment is performed. In the present disclosure, the sulfonic acid group (-SO ₃ H) and the functional group (-SO ₃ Na) as sodium sulfonate may be mentioned without distinction.

As such a triphenylmethane-based dye, Japanese Patent Application Laid-Open Nos. 2002-014222, 2003-246935, 2003-246935, 2008-304766, Japanese Patent Application Publication No. 2010-256598, Japanese Patent Application Publication No. 2011-200560, Japanese Patent Application Publication No. 2011-186043, Japanese Patent Application Publication No. 2012-173399, Japanese Patent Application Publication No. 2012-233033, Japanese Patent Application Publication No. 2012-098522, Japanese Patent Application Publication No. 2012-288970, Japanese Patent Application Publication No. 2012-200469, Japanese Patent Application Publication No. 2014-196262, International Publication No. 2010/123071 Manual, International Publicly known technologies described in Publication No. 2011/162217, International Publication No. 2013/108591, etc.

In one embodiment, the triphenylmethane-based dye is preferably C.I. Acid Violet 15, C.I. Acid Violet 17, C.I. Acid Violet 19, C.I. Acid Violet 21, C.I. Acid Violet 24, C.I. Acid Violet 25, C.I. Acid Violet 38, C.I. acid violet 49, C.I. acid blue 1, C.I. acid blue 3, C.I. acid blue 5, C.I. acid blue 7, C.I. acid blue 9, C.I. acid blue 11, C.I. acid blue 13, C.I. acid blue 15, C.I. acid blue 17, C.I. Acid Blue 22, C.I. Acid Blue 24, C.I. Acid Blue 26, C.I. Acid Blue 75, C.I. Acid Blue 83, C.I. Acid Blue 90, C.I. Acid Blue 93, C.I. Acid Blue 100, C.I. Basic Blue 81, C.I. Basic Blue 83.

Alternatively, as the triarylmethane-based dye, C.I. Basic Violet 1, C.I. Basic Violet 2, C.I. Basic Violet 3, C.I. Basic Violet 4, C.I. Basic Violet 14, C.I. Basic Blue 1, C.I. Alkali can be preferably used. C.I. basic blue 5, C.I. basic blue 7, C.I. basic blue 11, C.I. basic blue 26.

[Cyanine dye]

The cyanine-based dye can be used without any restriction as long as it is a compound having a pigment moiety including a cyanine skeleton in the molecule.

Examples of cyanine dyes include: C.I. basic yellow 11, 12, 13, 14, 21, 22, 23, 24, 28, 29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52, 53; C.I. basic red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68; C.I. basic violet 7, 15, 16, 20, 21, 39, 40; C.I. Alkaline Orange 27, 42, 44, 46; C.I. Alkaline Blue 62, 63, etc.

In addition, cyanine-based dyes described in Japanese Patent Laid-Open No. 2014-224970, Japanese Patent Laid-Open No. 2013-261614, etc. can also be used.

[Anthraquinone dye]

Anthraquinone-based dyes are dyes having an anthraquinone skeleton in the molecule.

Examples of anthraquinone dyes include: C.I. Solvent Yellow 117, 163, 167, 189; C.I. Solvent Orange 77, 86; C.I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; C.I. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105 , 111, 112, 122, 128, 132, 136, 139; C.I. solvent green 3, 28, 29, 32, 33; C.I. acid red 80; C.I. acid green 25, 27, 28, 41; C.I. acid violet 34; C.I. Acid blue 25, 27, 40, 45, 78, 80, 112; C.I. disperse yellow 51; C.I. disperse violet 26, 27; C.I. disperse blue 1, 14, 56, 60; C.I. direct blue 40; C.I. mordant red 3, 11 ; C.I. Mordant Blue 8, etc. In addition, Japanese Patent Application Laid-Open No. 9-291237, International Publication No. 2003/080734 Manual, International Publication No. 2006/024617 Manual, Japanese Patent Application Publication No. 2011-174987, Japanese Patent Application Publication No. 2013-53273 The anthraquinone dye described in Publication No. 1, etc. is used as a publicly known technology. The anthraquinone dye is preferably one dissolved in an organic solvent, and more preferably a blue, purple or red anthraquinone dye. From the viewpoint of brightness or contrast, preferred anthraquinone dyes are C.I. Solvent Blue 35, C.I. Solvent Blue 45, C.I. Acid Blue 80, C.I. Solvent Blue 104, and C.I. Solvent Blue 122.

In one embodiment, the anthraquinone-based dye is preferably C.I. Acid Violet 29, C.I. Acid Violet 31, C.I. Acid Violet 33, C.I. Acid Violet 34, C.I. Acid Violet 36, C.I. Acid Violet 39, C.I. Acid Violet 43, C.I. Acid Violet Violet 48, C.I. Acid Violet 63, C.I. Acid Violet 109, C.I. Acid Blue 25, C.I. Acid Blue 27, C.I. Acid Blue 41, C.I. Acid Blue 45, C.I. Acid Blue 62, C.I. Acid Blue 80, C.I. Acid Blue 127, C.I. Acid Blue 129, C.I. Acid Blue 145, C.I. Acid Blue 225, C.I. Acid Blue 230, C.I. Acid Blue 260, C.I. Acid Blue 264, C.I. Acid Blue 277, C.I. Acid Blue 281, C.I. Acid Blue 324 or C.I. Acid Blue 350.

In recent years, in order to improve the color reproduction characteristics and thinness of color filters, , it is necessary to increase the colorant content in the photosensitive coloring composition.

When used in a color liquid crystal display device, the content of the colorant (D) is preferably 20% by weight based on 100% by weight of the solid content of the photosensitive coloring composition for color filters according to the embodiment of the present invention. When the content is above, more preferably 30% by weight or more, particularly preferably 35% by weight or more, sufficient color reproducibility can be obtained and the film thickness can be reduced. In addition, if it is preferably 60% by weight or less, more preferably 50% by weight or less, and particularly preferably 45% by weight or less, the content of the resin or photopolymerizable compound as the curing material becomes reasonable and a sufficient cured coating can be obtained. membrane.

In addition, when used in an organic EL display device, the content of the colorant (D) is preferably 40% based on 100% by weight of the solid content of the photosensitive coloring composition for color filters according to the embodiment of the present invention. If it is 45% by weight or more, more preferably 45% by weight or more, sufficient color reproducibility can be obtained and the film thickness can be reduced. In addition, if it is preferably 60% by weight or less, more preferably 55% by weight or less, the content of the resin or photopolymerizable compound as the curing material becomes reasonable, and a sufficient cured coating film can be obtained.

<Dispersant>

Generally speaking, a dispersant has a structure that has both a site that is adsorbed to the colorant and a site that has high affinity for the solvent that serves as the colorant carrier and dispersion medium. The performance of the dispersant depends on the balance of these two sites. That is, in order to express dispersibility, the ability of the dispersant to adsorb the colorant and the affinity for the solvent serving as the colorant carrier and dispersion medium are both very important. The so-called colorant carrier mentioned here includes the resin or its precursor or the resin except the colorant component and the dispersant from the solid content. some mixture.

The dispersant that can be contained in the photosensitive coloring composition according to the embodiment of the present invention includes the dispersant (X) and/or other dispersants, and these dispersants can be used alone or in mixture of two or more kinds.

The dispersant having an oxetane group can be realized by the dispersant (X) or other dispersants having this structure. Since the dispersant has an oxetane group, the colored composition containing the dispersant has excellent heat resistance after curing.

In addition, the dispersant (X) described below is composed of two parts, X1' and X2'. It is impossible or simply impractical to determine and describe how these parts are bonded, so the manufacturing method is described.

"Dispersant (X)"

The dispersant (X) has a polyester part It is formed by reacting the hydroxyl group in a) and has a carboxyl group; and the vinyl polymer part X2' is formed by free radical polymerization of the ethylenically unsaturated monomer (c).

Here, the polyester portion X1' of the main chain functions as a colorant adsorption group, and the vinyl polymer portion X2' of the side chain functions as a colorant carrier affinity group, thereby suppressing colorant aggregation and obtaining stability. Excellent dispersion.

The content of the dispersant (X) is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 60 parts by weight, and further preferably 5 to 40 parts by weight based on 100 parts by weight of the colorant. When the content of the dispersant (X) is within this range, it can be made into one having excellent dispersibility and resistance.

In addition, the weight average molecular weight of the dispersant (X) is preferably 2,000 to 100,000.

If the weight average molecular weight is less than 2,000, the stability of the pigment composition may decrease. If it exceeds 100,000, the interaction between resins may be enhanced and the coloring composition may become thickened. In addition, the acid value of the obtained dispersant is preferably 5 mgKOH/g~200 mgKOH/g. More preferably, it is 5mgKOH/g~150mgKOH/g, and particularly optimal is 5mgKOH/g~100mgKOH/g. If the acid value is less than 5 mgKOH/g, the adsorption capacity for the colorant may be reduced and dispersion problems may occur. If it exceeds 200 mgKOH/g, the interaction between resins may be enhanced and the viscosity of the coloring composition may become high.

Next, each component of the dispersant (X) will be described.

[Hydroxy-containing compound (a)]

The hydroxyl-containing compound is not particularly limited as long as it has a hydroxyl group in the molecule. A polyol having two or more hydroxyl groups in the molecule is preferred, and a compound having two hydroxyl groups and a thiol group in the molecule is particularly preferred ( a1).

[Compound (a1) having two hydroxyl groups and one thiol group in the molecule]

Examples of the compound (a1) having two hydroxyl groups and one thiol group in the molecule include: 1-mercapto-1,1-methanediol, 1-mercapto-1, 1-Ethylene glycol (1-mercapto-1,1-ethanediol), 3-mercapto-1,2-propanediol (thioglycerol), 2-mercapto-1,2 -Propylene glycol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2 -Methyl-1,3-propanediol or 2-mercaptoethyl-2-ethyl-1,3- Propylene glycol, etc.

[Other polyols (a2)]

If only the particularly representative ones are exemplified as other polyols (a2) that can be used, there are polyols belonging to the following groups (1) to (7). By using these polyol compounds together, the density of carboxylic acid groups or the ratio of solvent-soluble parts can be easily adjusted.

Examples include: (1) ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1, 3-Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (Hydroxymethyl)cyclohexane, bisphenol A, hydrogenated bisphenol A, hydroxytrimethylacetylhydroxytrimethylacetate, trimethylolethane, trimethylolpropane, 2,2, 4-Trimethyl-1,3-pentanediol, glycerol or hexanetriol and other polyols; (2) Polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene diol Alcohol, polyoxypropylene polyoxytetramethylene glycol or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol and other polyether glycols; (3) By the various polyols and epoxy Compounds containing (cyclic) ether bonds such as ethane, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl glycidyl ether Modified polyether polyols obtained by ring-opening polymerization; (4) polyols, which are polyester polyols obtained by co-condensation of one or more of the various polyols and polycarboxylic acids, and special for use Succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citric acid Conic acid, itaconic acid, glutenedioic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2, Obtained from polycarboxylic acids represented by 5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid; (5) by the various polyvalent carboxylic acids Lactone-based polyester polyols obtained by the polycondensation reaction of one or more alcohols with various lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone, or Lactone-modified polyester polyols obtained from the polycondensation reaction of various polyols, polycarboxylic acids and various lactones; (6) When synthesizing polyester polyols, use more than one bisphenol A Epoxy compounds such as epoxy compounds, hydrogenated bisphenol A epoxy compounds, glycidyl ethers of monohydric alcohols and/or polyhydric alcohols, or glycidyl esters of monobasic and/or polybasic acids Polyester polyols; or (7) polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polyprene polyol, castor oil, castor oil derivatives, hydrogenated castor oil, Hydrogenated castor oil derivatives, hydroxyl-containing acrylic copolymers, hydroxyl-containing fluorine-containing compounds, or other polymer polyols such as hydroxyl-containing silicone resins.

Of course, the optionally added other polyols (a2) shown in these (1) to (7) can be used alone, or two or more types can be used in combination. From the viewpoint of compatibility or dispersion stability, the weight average The molecular weight is preferably 40 to 10,000, more preferably 100 to 2,000, still more preferably 100 to 1,000. If the weight average molecular weight is less than 40, the effect of improving compatibility or dispersion stability may become smaller. If it is 10,000 or more, the compatibility may actually become worse.

The number of hydroxyl groups in one molecule of the other polyol (a2) is not particularly limited as long as the target dispersant can be synthesized, but a diol is preferred. In particular, by reacting with tetracarboxylic dianhydride (b1), the carboxyl groups as pigment adsorption groups can be regularly arranged in the main chain, which is beneficial to pigment dispersion. If a polyol having more than two hydroxyl groups is used in large amounts, the main chain of the polyester may branch and become complicated and the volume may increase, making it difficult to obtain a dispersion effect. In order to adjust the molecular weight of the polyester part X1', adjust the viscosity of the dispersion, etc., it should be kept to a minimum from a design point of view.

[Acid anhydride (b)]

The acid anhydride (b) preferably contains one or more types selected from the group consisting of tetracarboxylic dianhydride (b1) and tricarboxylic anhydride (b2).

By reacting with the hydroxyl group of the hydroxyl-containing compound (a), the two acid anhydride groups of the tetracarboxylic dianhydride (b1) can regularly arrange the carboxyl groups as pigment adsorption groups on the main chain of the dispersant (X), which is advantageous Dispersed in pigments.

Moreover, when tricarboxylic anhydride (b2) is used, it may react with a hydroxyl group to form an ester bond, and a carboxyl group may remain.

Moreover, it is also possible to use together the anhydride of a compound which is a polycarboxylic anhydride other than tetracarboxylic dianhydride (b1) and tricarboxylic anhydride (b2), a dicarboxylic anhydride, and a compound which has 5 or more carboxylic acids.

[Tetracarboxylic dianhydride (b1)]

Tetracarboxylic dianhydride (b1) includes: 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-di Methyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride Anhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3 -Methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and other fats Tetracarboxylic dianhydride; pyromellitic dianhydride, ethylene glycol trimellitic anhydride ester, propylene glycol trimellitic anhydride ester, butylene glycol trimellitic anhydride ester, 3,3',4,4 '-Benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3 ,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid Carboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4 -Dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsebane dianhydride, 4,4'-bis(3,4- Dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropyldiphthalic anhydride, 3,3',4,4'-biphenyltetrakis Carboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride Formic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride , 9,9-bis(3,4-dicarboxyphenyl)bendicanhydride, 9,9-bis[4-(3,4-dicarboxyphenyloxy)phenyl]bendicanhydride, 3,4- Dicarboxy-1,2,3,4-tetrahydro-1-naphthyrosuccinic dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene Succinic dianhydride and other aromatic tetracarboxylic dianhydrides.

The tetracarboxylic dianhydride is not limited to the above-exemplified compounds, and may have any structure as long as it has two carboxylic acid anhydride groups. These can be used individually or in combination. Tetracarboxylic dianhydride is formed into polyester with two carboxyl groups in one unit by reacting with polyol. As a dispersant, from the viewpoint of pigment adsorption, it is preferred as a component of the dispersant (X).

Furthermore, from the viewpoint of the adsorption property to the colorant, aromatic tetracarboxylic dianhydride is preferably used, and tetracarboxylic dianhydride having two or more aromatic rings is more preferably used. Aromatic carboxylic acids have higher pigment adsorption capacity than aliphatic carboxylic acids. Carboxylic acids with two or more aromatic rings provide a suitable skeleton for pigment adsorption and also have high heat resistance.

Specific examples include aromatic tetracarboxylic dianhydride represented by the following general formula (7) or general formula (8).

[In general formula (7), k is 1 or 2. ]

General formula (8): [Chemical formula 10]

[In the general formula (8), Q ₁ is a direct bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -. From the general formula (9 ):

The group represented by the general formula (10): [Chemical 12]

represented group. ]

[Tricarboxylic anhydride (b2)]

Examples of the tricarboxylic acid anhydride (b2) include aliphatic tricarboxylic acid anhydride, aromatic tricarboxylic acid anhydride, and the like.

Examples of aliphatic tricarboxylic anhydrides include 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, and cis-propylene-1,2,3- Tricarboxylic acid-1,2-anhydride, 1,3,4-cyclopentanetricarboxylic anhydride, etc.

Examples of aromatic tricarboxylic anhydrides include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydride (1 ,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3,4,4 '-Benzophenone tricarboxylic anhydride, 3,4,4'-biphenyl ether tricarboxylic anhydride, 3,4,4'-biphenyl tricarboxylic anhydride, 2,3,2'-biphenyl tricarboxylic anhydride Carboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, or 3,4,4'-biphenylmethanetricarboxylic acid anhydride, etc. From the viewpoint of adsorption to pigments, the above-mentioned aromatic tricarboxylic anhydrides are preferably used.

One or more types selected from tetracarboxylic dianhydride (b1) and tricarboxylic anhydride (b2) The ratio of the acid anhydride group in the acid anhydride (b) to the hydroxyl group in the hydroxyl-containing compound (a) is preferably an acid anhydride group/hydroxyl group of 0.5 to 1.5.

When it is less than 0.5 and when it is greater than 1.5, in most cases the number of parts that do not react increases, and the target dispersant cannot be obtained.

[Ethylenically unsaturated monomer (c)]

The dispersant (X) has a vinyl polymer site X2' obtained by radically polymerizing the ethylenically unsaturated monomer (c). The ethylenically unsaturated monomer (c) contains an ethylenically unsaturated monomer (c1) having an oxetanyl group or other ethylenically unsaturated monomers, and two or more of these may be mixed and used. .

[Ethylenically unsaturated monomer (c1) having an oxetanyl group]

By copolymerizing the ethylenically unsaturated monomer (c1) having an oxetanyl group, the oxetanyl group can be introduced into the vinyl polymer part X2'.

The content of the ethylenically unsaturated monomer (c1) having an oxetanyl group is preferably 5 wt% based on the total of all ethylenically unsaturated monomers (c) (100% by weight). ~70% by weight, more preferably 10% by weight~50% by weight. If the content is 5% by weight or more, crosslinking properties will be excellent and the resistance will be better, and if the content is 70% by weight or less, stability will be excellent.

Examples of the ethylenically unsaturated monomer (c1) having an oxetanyl group include (meth)acrylic acid (3-methyl-3-oxetanyl)methyl ester, (meth)acrylic acid (3 -Ethyl-3-oxetanyl)methyl ester, (meth)acrylic acid (3-butyl-3-oxetanyl)methyl ester, (meth)acrylic acid (3-hexyl-3-oxo) Heterocyclobutyl) methyl ester, etc.

Examples of commercially available products include: ETERNACOLL, OXMA (manufactured by Mobe Kosan Co., Ltd.), OXE-10, OXE-30 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc.

[Other ethylenically unsaturated monomers]

Other ethylenically unsaturated monomers, in addition to the ethylenically unsaturated monomer (c1), include, for example: (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid normal Propyl ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate , stearyl (meth)acrylate, lauryl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate and other (meth)acrylic acid alkyl esters ; Aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, etc. Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate; alkanes such as methoxy polypropylene glycol (meth)acrylate and ethoxy polyethylene glycol (meth)acrylate Oxypolyalkylene glycol (meth)acrylates; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide N-substituted (meth)acrylamides such as amine, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, acrylmorpholine; N,N-dimethyl Amino-containing (meth)acrylates such as aminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; and nitriles such as (meth)acrylonitrile class. In addition, here, (meth)acrylate means methacrylate or acrylate, and (meth)acrylamide means methacrylamide. enamide or acrylamide.

In addition, monomers that can be used in combination with the acrylic monomer include styrenes such as styrene and α-methylstyrene; ethyl vinyl ether, n-propyl vinyl ether, and isopropyl vinyl ether. Vinyl ethers such as ether, n-butyl vinyl ether and isobutyl vinyl ether; fatty acid vinyl esters such as vinyl acetate and vinyl propionate.

[Synthesis method of dispersant (X)]

Examples of the synthesis method of the dispersant (X) include the following synthesis methods (1) to (2), but are not limited thereto.

[Synthesis method (1)]

The hydroxyl group in the vinyl polymer having two hydroxyl groups in a single terminal region, which is obtained by subjecting the ethylenically unsaturated monomer (c) to radical polymerization in the presence of the hydroxyl-containing compound (a), and the selected The dispersant (X) can be obtained by reacting the acid anhydride group in one or more acid anhydrides (b) of tetracarboxylic dianhydride (b1) and tricarboxylic anhydride (b2).

[Synthesis method (2)]

A compound produced by reacting a hydroxyl group in a hydroxyl-containing compound (a) and an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic dianhydride (b1) and tricarboxylic anhydride (b2) The dispersant (X) can be obtained by subjecting the ethylenically unsaturated monomer (c) to radical polymerization in the presence of ethylenic unsaturated monomer (c).

[Synthesis of polyester part X1']

The polyester part reaction steps.

(reaction catalyst)

As the catalyst used for the production of the polyester part X1', a known catalyst can be used. Examples of the catalyst include: triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, and 1,8-diazabicyclo-[5.4.0]-7 -Undecene, or tertiary amine compounds such as 1,5-diazabicyclo-[4.3.0]-5-nonene; or mono-n-butyl tin (IV) oxide, etc.

(reaction solvent)

In the production of the polyester part X1', it can also be produced using only the raw materials listed above. However, in order to avoid problems such as high viscosity and uneven reaction, it is preferable to use a solvent. The solvent used is not particularly limited, and known solvents can be used. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, toluene, xylene, or acetonitrile. The solvent used in the reaction can be removed by distillation or other operations after the reaction, or can be directly used as a solvent in the next step or as part of the product.

(reaction temperature)

The reaction temperature for the synthesis of the polyester part X1' is within the range of 50°C to 180°C, preferably 80°C to 140°C. If the reaction temperature is 50° C. or lower, the reaction rate may be slowed down. If the reaction temperature is 180° C. or higher, the carboxyl group and the hydroxyl group may undergo an esterification reaction, resulting in a decrease in acid value or gelation. Regarding the cessation of the reaction, the ideal is It is allowed to react until the absorption of the acid anhydride disappears due to infrared absorption. However, the reaction can also be stopped when more than 97% of the acid anhydride is half-esterified by measuring the acid value.

[Synthesis of vinyl polymer part X2']

The vinyl polymer part X2' in the dispersant (X) is obtained by radical polymerization of the ethylenically unsaturated monomer (c). Since the vinyl polymer portion X2' functions as a side chain of the dispersant (X) and as an affinity site for the solvent and colorant carrier, it can also be used when fine pigments are used or when dyes are used. Can be made into one with excellent stability.

The weight average molecular weight of the vinyl polymer part X2' is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, further preferably 2,000 to 12,000, particularly preferably 3,000 to 8,000. This portion X2' becomes an affinity portion for the solvent as the dispersion medium. If the weight average molecular weight of the vinyl polymer part X2' is less than 1,000, the steric repulsive effect of the solvent-friendly part may be reduced, and it may be difficult to prevent pigment aggregation, resulting in insufficient dispersion stability. In addition, if it exceeds 20,000, the absolute amount of the solvent-friendly portion increases and the dispersibility effect itself may decrease. Furthermore, the viscosity of the dispersion may become high.

In addition, the content of the ethylenically unsaturated monomer (c) is preferably 3 to 100 parts by weight relative to 1 part by weight of the hydroxyl-containing compound (a), and block polymerization or solution polymerization is performed. More preferably, it is 8 to 25 parts by weight, and still more preferably 10 to 20 parts by weight. If it exceeds 100 parts by weight, the following may occur: the molecular weight of the vinyl polymer part X2' is too high, and its absolute amount increases as the affinity part for the pigment carrier and solvent, thereby reducing the dispersion effect itself. If it is insufficient 10 parts by weight, the following may occur: the molecular weight of the vinyl polymer part X2' is too low, and as an affinity part for the pigment carrier and solvent, its stereorepulsive effect disappears, and it is difficult to suppress pigment aggregation.

During polymerization, 0.001 to 5 parts by weight of the polymerization initiator can be used arbitrarily with respect to 100 parts by weight of the ethylenically unsaturated monomer. Azo compounds and organic peroxides can be used as the polymerization initiator. Examples of azo compounds include: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane) 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) ), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2 -hydroxymethylpropionitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], etc. Examples of organic peroxides include: benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, Di(2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxytrimethylacetate, (3,5,5-trimethylhexyl acyl peroxide, dipropyl peroxide, diethyl peroxide, etc. These polymerization initiators may be used alone or in combination of two or more.

In the case of solution polymerization, the polymerization solvent can be ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, and propylene glycol monomethyl ether. Acetate, etc., but are not particularly limited to these. These polymerization solvents can also be used in mixture of two or more types.

As the dispersant (X), International Publication No. 2008/007776 Manual, Japanese Patent Application Publication No. 2009-155406, and Japanese Patent Application Publication No. 2011-157416 can be used. Known technologies described in gazettes, etc.

"Other dispersants"

For other dispersants, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid ammonium salt, polycarboxylic acid ammonium salt, etc. can be used. Carboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic acid esters, or modified products thereof, by poly(lower alkylene imine) and Oily dispersants such as amide or its salt formed by the reaction of polyester with free carboxyl groups, (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-cis Butenedioic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and other water-soluble resins or water-soluble polymer compounds, polyester series, modified polyacrylate series, ethylene oxide/propylene oxide addition compounds , phosphate esters, various surfactants, etc., these may be used alone or in combination of two or more, but are not necessarily limited to these.

The resin-type pigment dispersant contains a pigment-affinity moiety that has the property of adsorbing the pigment and a moiety that is compatible with the pigment carrier, and functions to adsorb the pigment and stabilize the dispersion of the pigment in the pigment carrier.

Commercially available resin dispersants include: Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140 manufactured by BYK-Chemie Japan. 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc.; SOLSPERSE manufactured by Japan's Lubrizol Company -3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000 , 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc.; EFKA-46 manufactured by BASF. 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc.; manufactured by Ajinomoto Fine-Techno Co., Ltd. Ajisper PA111, PB711, PB821, PB822, PB824, etc.

Examples of surfactants include: polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate , Monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether Anionic surfactants such as phosphate esters; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monoanhydride Nonionic surfactants such as stearate and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adducts; alkyl dimethyl Amphoteric surfactants such as alkyl betaine such as aminoacetic acid betaine and alkyl imidazoline. The other dispersant can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the colorant (D).

<Silane Coupling Agent (S)>

In order to improve the adhesion with the transparent substrate, the photosensitive coloring composition according to the embodiment of the present invention may contain an adhesion accelerator such as a silane coupling agent. By improving the adhesion with the silane coupling agent, the reproducibility of fine lines is good and the resolution is improved.

Examples of silane coupling agents include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane; γ-methacryloxypropyl Trimethoxysilane and other (meth)acrylic silanes; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane Silane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyl Epoxysilanes such as trimethoxysilane, γ-glycidoxypropyltriethoxysilane; N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl) Ethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, Aminosilanes such as γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane; γ -Thiosilanes such as mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant (D) in the photosensitive coloring composition.

<Polyfunctional thiol (F)>

The photosensitive coloring composition according to the embodiment of the present invention may contain polyfunctional thiol (F). Polyfunctional thiol (F) is a compound having two or more thiol (SH) groups.

The polyfunctional thiol (F) is used together with the photopolymerization initiator (A), thereby acting as a chain transfer agent in the free radical polymerization process after light irradiation, and is less susceptible to polymerization caused by oxygen. The photosensitive coloring composition obtained is highly sensitive because it blocks thiyl radicals. Particularly preferred are polyfunctional aliphatic thiols in which SH groups are bonded to aliphatic groups such as methylene and ethylidene groups.

Examples include: hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioacetate, ethylene glycol dithiopropionate Acetate, ethylene glycol dithiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithiopropionate, trimethylolethane tris(3-mercaptobutanate) acid ester), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrathioacetate, pentaerythritol tetrathiopropionate, Pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene , 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. These polyfunctional thiols can be used individually by 1 type, or in mixture of 2 or more types.

The content of the polyfunctional thiol (F) is preferably 0.05 to 100 parts by weight, and more preferably 1.0 to 50.0 parts by weight relative to 100 parts by weight of the colorant (D).

By using 0.05 parts by weight or more of polyfunctional thiol, better development resistance can be obtained. In the case of using a monofunctional thiol having one thiol (SH) group, such improvement in development resistance cannot be obtained.

<Antioxidant (G)>

The photosensitive coloring composition according to the embodiment of the present invention may contain an antioxidant. Antioxidants prevent the photopolymerization initiator or thermosetting compound contained in the coloring composition for color filters from oxidizing and yellowing due to thermal hardening or the thermal step during annealing of indium tin oxide (ITO). , thus improving the transmittance of the coating film. Therefore, by including an antioxidant, yellowing caused by oxidation during the heating step can be prevented, thereby obtaining a high coating film transmittance.

The "antioxidant" in the embodiment of the present invention may be a compound having an ultraviolet absorbing function, a free radical supplementing function, or a peroxide decomposing function. Specifically, examples of the antioxidant include hindered phenols and hindered amines. As compounds of the type, phosphorus type, sulfur type, benzotriazole type, benzophenone type, hydroxylamine type, salicylate type and triazine type, well-known ultraviolet absorbers, antioxidants, etc. can be used.

From the viewpoint of balancing the transmittance and sensitivity of the coating film, preferred ones among these antioxidants include hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants. Moreover, a hindered phenol antioxidant, a hindered amine antioxidant, or a phosphorus antioxidant is more preferable.

These antioxidants can be used individually by 1 type, or may mix and use 2 or more types in arbitrary ratios as needed.

Based on the solid content weight of the photosensitive coloring composition (100% by weight), when the content of the antioxidant is 0.5% by weight to 5.0% by weight, it is more preferable because the brightness and sensitivity are good.

<UV absorber (G), polymerization inhibitor (H)>

The photosensitive colored composition according to the embodiment of the present invention may contain an ultraviolet absorber (G) or a polymerization inhibitor (H). By containing an ultraviolet absorber (G) or a polymerization inhibitor (H), the shape and resolution of the pattern can be controlled. Examples of ultraviolet absorbers include: 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis (2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6- Bis(4-phenylphenyl)-1,3,5-triazine and other hydroxyphenyltriazine series; 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2H- Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl) )-5-chlorobenzotriazole and other benzotriazole series; 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2',4,4' -Benzophenones such as tetrahydroxybenzophenone; salicylate esters such as phenyl salicate and p-tert-butylphenyl salicylate; ethyl-2-cyano-3,3'-diphenyl Cyanoacrylate series such as acrylate; 2,2,6,6-tetramethylpiperidin-1-oxy (triacetone-amine-N-oxy), bis(2,2,6,6-tetramethyl Methyl-4-piperidyl-sebacate, poly[6-[(1,1,3,3-tetrabutyl)amino]-1,3,5-triazine-2 , 4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl)imino] and other hindered amine systems, etc. These are used alone or in combination. Examples of polymerization inhibitors include methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, and 4-methoxy -Hydroquinone derivatives and phenolic compounds such as 1-naphthol and tert-butylcatechol; phethiazide, bis-(1-dimethylbenzyl)phethiazide, 3,7-dioctylphethiazide Amine compounds such as oxazine; copper and manganese salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate. ; 4-Nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine, etc. Nitroso compounds and their ammonium salts, aluminum salts, etc. are used individually or in mixture.

The ultraviolet absorber (G) and the polymerization inhibitor (H) may be in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight relative to 100 parts by weight of the colorant (D) in the coloring composition. to use.

By using 0.01 parts by weight or more of the ultraviolet absorber (G) or polymerization inhibitor (H), better resolution can be obtained.

<Solvent>

In order to fully disperse the colorant (D) in a pigment carrier such as the resin (B) or the photopolymerizable compound (C), and apply it to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 μm to 10 μm, Thereby, a filter segment or a black matrix can be easily formed, and the photosensitive coloring composition which concerns on embodiment of this invention may contain a solvent. Examples of solvents include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3- Butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1- Ketone, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1 -Butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, 2nd butylbenzene, 3rd butylbenzene, γ-butyrolactone, isobutyl Alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl Ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol Alcohol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diisobutyl ketone Ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethyl ether Glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, Dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol mono Methyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol mono Methyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isoacetate Butyl ester, propyl acetate, dibasic acid ester, etc. are used individually or in mixture.

The solvent can be used in an amount of 100 to 10,000 parts by weight, preferably 500 to 5,000 parts by weight relative to 100 parts by weight of the colorant (D) in the photosensitive coloring composition.

<Other ingredients>

<Storage Stabilizer>

The photosensitive coloring composition according to the embodiment of the present invention may contain storage-stable agent. By containing a storage stabilizer, the viscosity of the composition can be stabilized over time. Examples of storage stabilizers include: 2,6-bis(1,1-dimethylethyl)-4-methylphenol, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4- Hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)1,3,5-tri Hindered phenols such as oxazine; organic phosphines such as tetraethylphosphine, triphenylphosphine, tetraphenylphosphine; zinc dimethyldithiophosphate, zinc dipropyldithiophosphate, dibutyldithiophosphate Phosphites such as molybdenum; sulfur series such as dodecyl sulfide and benzothiophene; quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxylamine; organic acids such as lactic acid and oxalic acid and their methyl ethers etc., these can be used alone or mixed.

The storage stabilizer can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the colorant (D) in the coloring composition.

By using 0.01 parts by weight or more of the storage stabilizer, the stability over time of the photosensitive coloring composition is improved.

In addition, the photosensitive coloring composition according to the embodiment of the present invention may contain an amine compound having an action of reducing dissolved oxygen.

Examples of such amine compounds include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethyl Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, etc.

<Production method of photosensitive coloring composition>

The photosensitive coloring composition according to the embodiment of the present invention can be produced as follows: Production: Use various dispersion means such as three-roller mill, two-roller mill, sand mill, kneader, grinder, etc. to finely disperse the colorant (D) together with the dispersant into the resin (B) and other pigments The pigment dispersion is prepared in a carrier and/or solvent, and in the pigment dispersion, the photopolymerization initiator (A), the resin (B), the photopolymerizable compound (C), and optionally other photopolymerization are initiated. Agent (Y), sensitizer (E), multifunctional thiol (F), ultraviolet absorber (G), polymerization inhibitor (H), storage stabilizer, solvent, and other ingredients are mixed and stirred. In addition, a photosensitive coloring composition containing two or more pigments can be produced by mixing each pigment dispersion finely dispersed in a pigment carrier and/or a solvent, and then adding a photopolymerization initiator (A) or the photopolymerizable compound (C), etc. are mixed and stirred.

When dispersing the colorant (D) in the resin (B) and/or the solvent, an appropriate pigment derivative and an optional dispersant may be included. Pigment derivatives are excellent in dispersing pigments and have a large effect in preventing re-aggregation of dispersed pigments. Therefore, when the following photosensitive coloring composition is used, a color filter excellent in transparency can be obtained. The composition is prepared by dispersing the pigment in the resin (B) and/or the solvent using a pigment derivative and an optional dispersant.

Pigment derivatives are compounds in which substituents are introduced into organic pigments. Organic pigments also include light yellow aromatic polycyclic compounds such as naphthalene-based and anthraquinone-based compounds that are not generally called pigments. Pigment derivatives that can be used are Japanese Patent Publication No. Sho 63-305173, Japanese Patent Publication No. Sho 57-15620, Japanese Patent Publication No. Sho 59-40172, Japanese Patent Publication No. Sho 63-17102, and Japanese Patent Publication No. Sho 63-17102. Those described in Public Gazette No. 5-9469, etc. can be used alone or combined Use a mixture of two or more.

The pigment derivative can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the colorant (D).

The photosensitive colored composition according to the embodiment of the present invention can be prepared in the form of a solvent-developable or alkali-developable colored resist material. The colored resist material is a composition in which a colorant (D) is dispersed together with an optional dispersant in an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (A), and a solvent. The one who comes from things.

The photosensitive coloring composition preferably removes coarse particles of 5 μm or more, preferably 1 μm or more, further preferably 0.5 μm or more, and mixed dust by centrifugal separation, a sintered filter, a membrane filter, or the like. .

<Color filter>

Next, the color filter of the present invention will be described.

The color filter according to the embodiment of the present invention includes filter segments or a black matrix formed of the photosensitive coloring composition of the present invention on a transparent substrate. A general color filter has at least one red filter segment, at least one green filter segment, and at least one blue filter segment, or may have at least one magenta filter segment and at least one indigo filter segment. light segments, and at least one yellow filter segment.

As the transparent substrate, glass plates such as soda-lime glass, low-alkali borosilicate glass, and alkali-free aluminoborosilicate glass, or resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate can be used. In addition, in order to drive the liquid crystal after the panel is formed, a layer containing indium oxide, tin oxide, etc. can also be formed on the surface of the glass plate or resin plate. of transparent electrodes.

The dry film thickness of the filter segment and the black matrix is preferably 0.2 μm ~ 10 μm, more preferably 0.2 μm ~ 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an infrared-ray (IR) oven, a heating plate, etc. can be used.

The formation of various color filter segments and black matrices by photolithography can be carried out as follows. That is, a photosensitive resist material prepared as a solvent-developable or alkali-developable colored resist material is applied by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 μm to 10 μm. The coloring composition is coated on the transparent substrate. If necessary, the dried film is exposed to ultraviolet rays through a mask having a prescribed pattern that is provided in contact or non-contact with the film.

After that, it is immersed in a solvent or alkali developer, or the developer is sprayed by spraying or the like to remove the unhardened portion and form the desired pattern, thereby forming the filter segments and the black matrix. Furthermore, in order to promote the polymerization of the filter segments and the black matrix formed by development, heating may also be performed if necessary. The photolithography method can form filter segments and black matrices with higher precision than the printing method.

During development, the alkali developer can use aqueous solutions such as sodium carbonate and sodium hydroxide, or organic bases such as dimethylbenzylamine and triethanolamine. In addition, defoaming agents or surfactants can also be added to the developer.

As the development treatment method, spray development method, spray development method, dip (dip) development method, puddle (liquid coating) development method, etc. can be applied.

Furthermore, in order to improve the ultraviolet exposure sensitivity, after the photosensitive coloring composition is applied and dried, a water-soluble resin or an alkali-soluble resin, such as polyvinyl alcohol or water After the soluble acrylic resin or the like is applied and dried to form a film that prevents polymerization inhibition by oxygen, ultraviolet exposure can be performed.

The present invention includes at least the following embodiments.

[1]

A photosensitive coloring composition characterized by containing: a photopolymerization initiator (A) represented by the following general formula (1), a resin (B), a photopolymerizable compound (C), and a colorant (D) .

[In the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkenyl group, Substituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclyl, substituted or unsubstituted heterocyclic oxy, substituted or unsubstituted alkylmercapto, substituted or unsubstituted arylmercapto, substituted or unsubstituted acyl, or substituted or unsubstituted Amino group. ]

[2]

The photosensitive coloring composition according to [1], characterized by further containing another photopolymerization initiator (Y).

[3]

The photosensitive coloring composition according to [2], characterized in that the other photopolymerization initiator (Y) contains at least one selected from the group consisting of an acetophenone-based compound, a phosphine-based compound, and an imidazole-based compound. A compound.

[4]

The photosensitive colored composition according to any one of [1] to [3], further comprising a silane coupling agent (S).

[5]

The photosensitive coloring composition according to any one of [1] to [4], characterized by further containing a polyfunctional thiol (F).

[6]

A color filter characterized by having filter segments or a black matrix formed of the photosensitive coloring composition as described in any one of [1] to [5] on a transparent substrate.

[7]

A photosensitive coloring composition characterized by containing the following general formula (1): The photopolymerization initiator (A), resin (B), photopolymerizable compound (C), colorant (D), and dispersant are shown, and are characterized in that they are selected from the group consisting of resin (B), colorant (D) ) and a dispersant have an oxetanyl group.

[In the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkenyl group, Substituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclyl, substituted or unsubstituted heterocyclic oxy, substituted or unsubstituted alkylmercapto, substituted or unsubstituted arylmercapto, substituted or unsubstituted acyl, or substituted or unsubstituted Amino group. ]

[8]

The photosensitive coloring composition according to [7], characterized in that the dispersant has an oxetane group, and the dispersant contains a dispersant (X), and the dispersant (X) has a polyester part and It has a carboxyl group; and the vinyl polymer part X2' is obtained by free radical polymerization of the ethylenically unsaturated monomer (c), and the part X2' has an oxetanyl group.

[9]

The photosensitive coloring composition according to [7] or [8], characterized by further containing another photopolymerization initiator (Y).

[10]

The photosensitive coloring composition according to [9], characterized in that the other photopolymerization initiator (Y) contains at least one selected from the group consisting of an acetophenone-based compound, a phosphine-based compound, and an imidazole-based compound. A compound.

[11]

The photosensitive coloring composition according to any one of [7] to [10], characterized by further containing a polyfunctional thiol (F).

[12]

A color filter characterized by having filter segments or a black matrix formed of the photosensitive colored composition according to any one of [7] to [11] on a transparent substrate.

[Example]

Hereinafter, embodiments of the present invention will be described in detail using examples. However, the present invention is not limited to the following examples.

The group of Examples 1 to 30 is described in the first half of the Examples section, and the group of Examples 31 to 52 is described in the second half. Regarding each group, first, the manufacturing method of the acrylic resin solution and the pigment dispersion used in the Examples and Comparative Examples will be described, and then the preparation and evaluation of the photosensitive coloring composition will be described. The molecular weight of the resin is: HLC-8220GPC (manufactured by Tosoh Co., Ltd.) is used as the device, two strings of TSK-GEL SUPER HZM-N are connected as the column, and tetrahydrofuran (THF) is used as the solvent The weight average molecular weight obtained in terms of polystyrene was measured. In the examples and comparative examples, "part" means "part by weight".

About Example 1~Example 30

<Production method of micronized green pigment>

(Green micronized pigment (G-2))

Add 500 parts of 98% sulfuric acid, 50 parts of phthalocyanine pigment represented by the following formula (7), 500 parts of N-methylpyrrolidone, and 13.9 parts of diphenyl phosphate to a three-necked flask, and heat to 90°C and allowed to react for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain phthalocyanine pigment G-2. The average primary particle diameter of the obtained pigment was 30 nm.

(Green micronized pigment (G-3))

500 parts of 98% sulfuric acid, 50 parts of phthalocyanine pigment represented by the following formula (7), 1,2-dibromo-5,5-dimethylhydantoin (1,2-dibromo-5,5 -dimethyl hydantoin, DBDMH) 129.3 parts was added to the three-necked flask and stirred to react at 20°C for 6 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3° C., and the precipitated solid was filtered and washed with water. 500 parts of 2.5% sodium hydroxide aqueous solution and the filtered residue were added to the beaker, and stirred at 80° C. for 1 hour. Thereafter, the mixture was filtered, washed with water, and dried to obtain a pigment in which an average of 10.1 bromine atoms were substituted on the phthalocyanine ring.

Next, add 500 parts of N-methylpyrrolidone, 50 parts of the obtained pigment with an average of 10.1 bromine atoms substituted on the phthalocyanine ring, and 13.9 parts of diphenyl phosphate into a three-necked flask, and heat to 90 ℃ and allowed to react for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain phthalocyanine pigment G-3. The average primary particle diameter of the obtained pigment was 30 nm.

Formula (7)[Chemistry 15]

<Production method of finely divided blue pigment>

(Blue micronized pigment (B-2))

90 parts of crude copper phthalocyanine synthesized by a known method and 10 parts of the dispersant represented by chemical formula (8) were added to 1000 parts of 98% sulfuric acid, stirred at 30°C for 2 hours, and then used an aspirator and 5000 parts of water were mixed to obtain an aqueous solution in which copper phthalocyanine particles were precipitated. The obtained aqueous solution was stirred for 30 minutes, filtered, washed with water, dried and pulverized to obtain 95 parts of blue pigment composition (B-2). For the obtained blue pigment composition (B-2), X-ray diffraction at 2θ=5° to 35° was confirmed using an X-ray diffraction device (RINT 2000 manufactured by Rigaku Corporation). pattern, as a result, characteristic peaks were confirmed for α-type copper phthalocyanine near 6.94° and 9.76°, but no characteristic peaks were confirmed for β-type copper phthalocyanine near 6.9°, 9.0°, and 12.4°. , so it was confirmed to be α-type copper phthalocyanine (C.I. Pigment Blue 15).

Formula (8)[Chemistry 16]

(Blue micronized pigment (B-3))

85 parts of crude copper phthalocyanine synthesized by a known method, 15 parts of the dispersant represented by chemical formula (8), 1000 parts of sodium chloride, and 280 parts of diethylene glycol were put into a stainless steel 1-gallon kneader manufactured by Inoue Seisakusho Co., Ltd. , mix at 70°C for 8 hours. After kneading, take out 20,000 parts of acetic acid-sodium acetate buffer aqueous solution (pH 4.0) at 45°C, keep it warm and stir for 1 hour, then filter, wash, dry, and pulverize to obtain a blue pigment composition (B-3). 96 copies. For the obtained blue pigment composition (B-3), X-ray diffraction at 2θ=5° to 35° was confirmed using an X-ray diffraction device (RINT 2000 manufactured by Rigaku Corporation). pattern, as a result, characteristic peaks were confirmed for β-type copper phthalocyanine near 6.9°, 9.0°, and 12.4°, but no characteristic peaks were confirmed for α-type copper phthalocyanine near 6.94° and 9.76°. , In addition, no characteristic peaks were confirmed in ε-type copper phthalocyanine near 7.5° and 9.1°, so it was confirmed to be β-type copper phthalocyanine (C.I. Pigment Blue 15:2).

<Production method of salt-forming compound V>

A salt-forming compound (V) containing C.I. Acid Red 52 and tristearylmonomethylammonium chloride as a quaternary ammonium salt compound was prepared in the following procedure. Dissolve C.I. Acid Red 52 in water to form a 10% aqueous solution. After heating to 30°C to 50°C, dissolve tristearylmonomethylammonium chloride to form a 5% solution and add it dropwise in small amounts. In methanol/water=20/80 solution. In addition, tristearylmonomethylammonium chloride can also be used as a solid. After adding tristearylmonomethylammonium chloride dropwise, the mixture was stirred at 30°C to 50°C for 3 hours to fully proceed with the reaction. Allow to cool to room temperature while stirring, then perform suction filtration. After washing with water, use a dryer to remove water and dry the salt-forming compound remaining on the filter paper to obtain C.I. Acid Red 52 and Tristearyl Monomethyl Chloride. Ammonium salt-forming compound, salt-forming compound (V).

<Production method of acrylic resin solution>

[Preparation of acrylic resin solution]

(Stage 1: Polymerization of the resin backbone)

Put 100 parts of propylene glycol monomethyl ether acetate (PGMAC) into a reaction vessel equipped with a thermometer, cooling tube, nitrogen introduction tube, and stirring device in a detachable four-necked flask, with one side facing the container While injecting nitrogen gas, heat to 120°C. At the same temperature, 14 parts of styrene, 29 parts of dicyclopentyl methacrylate, 57 parts of glycidyl methacrylate, and as the The precursor reaction in the stage requires a mixture of 1.0 parts of azobisisobutyronitrile as the catalyst to perform the polymerization reaction.

(Stage 2: Reaction in epoxy groups)

Next, the air in the flask was replaced, 29 parts of acrylic acid was put in and as this stage The catalyst required for the reaction of the precursors is 0.3 parts of tri-dimethylaminomethylphenol and 0.3 parts of hydroquinone. The reaction is carried out at 120°C for 5 hours to obtain a weight average molecular weight (Mw) of about 10500. of resin solution. The added acrylic acid is ester-bonded to the epoxy terminal of the glycidyl methacrylate structural unit, so no carboxyl group is generated in the resin structure.

(Stage 3: Reaction in hydroxyl group)

Furthermore, 46 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine, which is a catalyst required for the precursor reaction in this stage, were added and reacted at 120° C. for 4 hours. Regarding the added tetrahydrophthalic anhydride, one of the two carboxyl groups generated by cleavage of the carboxylic anhydride site is ester-bonded to the hydroxyl group in the resin structure, and the other generates a carboxyl terminal.

(Phase 4: Adjustment of non-volatile components)

Propylene glycol monomethyl ether acetate was added so that the non-volatile content would be 20% by weight to obtain an acrylic resin solution. The weight average molecular weight (Mw) is 11500, and the acid value is 103 mgKOH/g.

<Production method of pigment dispersion>

[Preparation of red pigment dispersion]

After the mixture of the following composition is stirred evenly, use an Eiger Mill ("mini model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 1 mm. After dispersing for 5 hours, it was filtered with a 5 μm filter to prepare a red pigment dispersion P-R.

Diketopyrrolopyrrole pigment (C.I. Pigment Red 254): 7.02 parts

("Irgaphor Red B-CF" manufactured by BASF)

Anthraquinone pigment (C.I. Pigment Red 177): 1.38 parts

("Cromophtal Red A2B" manufactured by BASF)

Nickel azo complex pigment (C.I. Pigment Yellow 150): 0.80 parts

("E4GN" manufactured by Lanxess)

Resin type pigment dispersant: 2.05 parts

("SOLSPERSE 20000" manufactured by Lubrizol Corporation of Japan)

Diketopyrrolopyrrole pigment derivative: 2.00 parts

Acrylic resin solution: 13.75 parts

Cyclohexanone: 73.00 parts

[Preparation of green pigment dispersion P-G1]

A green pigment dispersion P-G1 was prepared in the same manner as the red pigment dispersion using a mixture of the following composition.

Zinc phthalocyanine pigment (C.I. Pigment Green 58): 8.95 parts

("FASTOGENGREEN A110" manufactured by DIC Corporation)

Monoazo pigment (C.I. Pigment Yellow 150): 2.75 parts

("E4GN" manufactured by Lanxess)

Resin type pigment dispersant: 4.90 parts

("EFKA 4300" manufactured by BASF Corporation)

Propylene glycol monomethyl ether acetate: 83.40 parts

[Preparation of green pigment dispersion P-G2]

A green pigment dispersion P-G2 was prepared in the same manner as the red pigment dispersion using a mixture of the following composition.

Phthalocyanine pigment G-2: 3.4 parts

Quinphthalone pigment (C.I. Pigment Yellow 138): 7.6 parts

("Paliotol Yellow K0961HD" manufactured by BASF)

Resin-type pigment dispersant ("BYK-LPN6919" manufactured by BYK-Chemie): 5.5 parts

Acrylic resin solution: 28.5 parts

Propylene glycol monomethyl ether acetate: 39.0 parts

Cyclohexanone: 16.0 parts

[Preparation of green pigment dispersion P-G3]

A green pigment dispersion P-G3 was prepared in the same manner as the red pigment dispersion using a mixture of the following composition.

Phthalocyanine pigment G-3: 3.4 parts

Quinphthalone pigment (C.I. Pigment Yellow 138): 7.6 parts

("Paliotol Yellow K0961HD" manufactured by BASF)

Resin-type pigment dispersant ("BYK-LPN6919" manufactured by BYK-Chemie): 5.5 parts

Acrylic resin solution: 28.5 parts

Propylene glycol monomethyl ether acetate: 39.0 parts

Cyclohexanone: 16.0 parts

[Preparation of blue pigment dispersion P-B1]

Using a mixture of the following composition, blue pigment dispersion P-B1 was prepared in the same manner as the red pigment dispersion.

ε-type copper phthalocyanine pigment (C.I. Pigment Blue 15:6): 11.20 parts

("Heliogen Blue (Heliogen Blue) L-6700F" manufactured by BASF)

Resin type pigment dispersant: 4.62 parts

("SOLSPERSE 20000" manufactured by Lubrizol Corporation of Japan)

Acrylic resin solution: 1.00 parts

Cyclohexanone: 83.18 parts

[Preparation of blue pigment dispersion P-B2]

Using a mixture of the following composition, blue pigment dispersion P-B2 was prepared in the same manner as the red pigment dispersion.

Blue pigment composition B-2: 11.20 parts

Resin type pigment dispersant: 4.62 parts

("SOLSPERSE 20000" manufactured by Lubrizol Corporation of Japan)

Acrylic resin solution: 1.00 parts

Cyclohexanone: 83.18 parts

[Preparation of blue pigment dispersion P-B3]

Using a mixture of the following composition, blue pigment dispersion P-B3 was prepared in the same manner as the red pigment dispersion.

Blue pigment composition B-3: 11.20 parts

Resin type pigment dispersant: 4.62 parts

("SOLSPERSE 20000" manufactured by Lubrizol Corporation of Japan)

Acrylic resin solution: 1.00 parts

Cyclohexanone: 83.18 parts

[Method for producing a resin solution containing a salt-forming compound]

(Preparation of resin solution (SV) containing salt-forming compound)

The following mixture was stirred and mixed until uniform, and then filtered with a 5.0 μm filter to prepare a resin solution (SV) containing a salt-forming compound.

Salt-forming compound (V): 5.00 parts

Acrylic resin solution: 50.00 parts

Cyclohexanone: 35.00 parts

Propylene glycol monomethyl ether acetate: 10.00 parts

[Preparation of black pigment dispersion]

Using a mixture of the following composition, black pigment dispersion P-BK was prepared in the same manner as the red pigment dispersion.

Carbon black ("MA77" manufactured by Mitsubishi Chemical Corporation): 11.20 parts

Resin type pigment dispersant: 3.82 parts

("SOLSPERSE 20000" manufactured by Lubrizol Corporation of Japan)

Acrylic resin solution: 4.90 parts

Cyclohexanone: 80.08 parts

(Preparation of photosensitive coloring composition)

Each material was mixed and stirred at the formula ratio shown in Tables 1 to 3, and filtered with a 1 μm filter to obtain photosensitive coloring compositions of each color.

[Table 1]

The symbols in Tables 1 to 3 are shown below.

． Photopolymerization initiator A1: a compound having the structure of the following formula (2)

． Photopolymerization initiator A2: a compound having the structure of the following formula (3)

． Photopolymerization initiator Y1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one

("Irgacure 907" manufactured by BASF)

． Photopolymerization initiator Y2: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1- Butanone

("Irgacure 379" manufactured by BASF)

． Photopolymerization initiator Y3: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO)

("Lucirin TPO" manufactured by BASF)

． Photopolymerization initiator Y4: 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole

("Bimidazole" manufactured by Kurogane Chemicals Co., Ltd.)

． Photopolymerization initiator Y5: ethane-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O- Acetyl oxime)

("Irgacure OXE02" manufactured by BASF)

． Sensitizer E1: 2,4-diethylthioxanthone

("Kayacure DETX-S" manufactured by Nippon Chemical Co., Ltd.)

． Sensitizer E2: 4,4'-bis(diethylamino)benzophenone

("EAB-F" manufactured by Hodogaya Chemical Industry Co., Ltd.)

． Photopolymerizable compound C: dipentaerythritol hexaacrylate

("Aronix M-402" manufactured by Toa Gosei Co., Ltd.)

． Silane coupling agent S1: 3-glycidoxypropylmethyldimethoxysilane

("Z-6044" manufactured by Toray.Dow Corning)

． Silane coupling agent S2: 3-methacryloxypropyltriethoxysilane

("KBE-503" manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

． Silane coupling agent S3: 3-acrylyloxypropyltrimethoxysilane

("KBM-5103" manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

． Polyfunctional thiol F1: trimethylolpropane tri(3-mercapto butyrate) (TPMB) ("TPMB" manufactured by Showa Denko Co., Ltd.)

． Polyfunctional thiol F2: pentaerythritol tetrakis(3-mercapto propionate) (PEMP) ("PEMP" manufactured by Sakai Chemical Industry Co., Ltd.)

． Antioxidant G1: pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] 4-hydroxyphenyl)propionate)

("IRGANOX 1010" manufactured by BASF)

． Polymerization inhibitor H1: methylhydroquinone (MH)

("MH" manufactured by Seiko Chemical Co., Ltd.)

． Organic solvent: cyclohexanone

The obtained photosensitive coloring composition was evaluated by the following method. The results are shown in Tables 4 to 6.

[Pattern formation of filter segments and black matrix]

The obtained photosensitive coloring composition was applied to a 10 cm × 10 cm of the glass substrate, heat it in a clean oven at 70°C for 15 minutes to remove the solvent, thereby obtaining a coating film of approximately 2 μm. Next, after the substrate was cooled to room temperature, ultraviolet light was exposed using an ultrahigh-pressure mercury lamp through a mask with stripe patterns of 100 μm wide (pitch 200 μm) and 25 μm wide (pitch 50 μm). Thereafter, the substrate was spray developed using a sodium carbonate aqueous solution at 23°C, washed with ion-exchange water, air-dried, and heated at 230°C for 30 minutes in a clean oven. Spray development is performed with the shortest time that can form a pattern without development residue for each coating film made of the photosensitive coloring composition, and this is set as a reasonable development time.

The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[Sensitivity evaluation]

The pattern film thickness of the 100 μm mask portion of the filter segment or black matrix formed by the above method was measured, and the minimum exposure amount after coating that was 90% or more relative to the film thickness was evaluated. The smaller the minimum exposure amount, the higher the sensitivity and the better the photosensitive coloring composition becomes.

The evaluation levels are as follows.

◎：Less than 30mJ/cm ²

○：30mJ/ ^cm2 or more and less than 50mJ/ ^cm2

△: 50mJ/cm ² or more and less than 100mJ/cm ²

×: 100mJ/cm2 ^or more

[Linearity evaluation]

Use an optical microscope to observe the filter segments or black matrices formed by the method. The pattern of the 100 μm mask part was evaluated. The evaluation levels are as follows.

○: Good linearity

△: Local linearity failure

×: Poor linearity

[Pattern shape evaluation]

The cross section of the pattern of the 100 μm mask portion of the filter segment or black matrix formed by the method was observed and evaluated using an electron microscope. The positive taper angle of the pattern profile is good. The evaluation levels are as follows.

◎: The cross section has a gentle positive cone shape.

○: The cross section has a positive cone angle shape

×: The cross section has an inverted tapered shape.

[Analytical evaluation]

The pattern of the 25 μm mask portion of the filter segment or black matrix formed by the method was observed using an optical microscope and evaluated. The evaluation levels are as follows. Poor resolution means that adjacent stripe patterns are connected or have defects. The evaluation levels are as follows.

◎: Excellent resolution and linearity

○: Slightly poor in linearity but good in resolution

△: Poor linearity, local defects occur

×: Poor analytical performance

[Evaluation of development resistance]

In spray development, develop the filter for twice as long as is reasonable. The pattern film thickness of the 100 μm mask portion of the segment or black matrix is measured and compared with the pattern film thickness formed by development with a reasonable development time. The evaluation levels are as follows.

◎: Film thickness difference within 20%

○: Film thickness difference is greater than 20% and within 40%

×: The film thickness difference is greater than 40%. Or become chipped or peeled off

[Chemical resistance evaluation]

The filter segment or black matrix formed by the above method is immersed in the N-methylpyrrolidone solution for 30 minutes, washed with ion-exchange water, air-dried, and the pattern of the 100 μm mask part is observed and evaluated using an optical microscope. . The evaluation levels are as follows.

◎: No change in appearance or color, considered good

○: Partially wrinkled, etc., but no change in color, considered good

×: peeling or fading occurs

As shown in Tables 4 to 6, the filter segments and black matrices formed using the photosensitive coloring compositions of Examples 1 to 30 have good sensitivity, linearity and resolution. The photopolymerization of the present application Examples 7 to 10, 12, 16 to 18, 21 to 23, and 27 to where the initiator (A) is used in combination with other photopolymerization initiator (Y) Pattern shape of Example 29 The shape shows better characteristics. The other photopolymerization initiator (Y) is 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl Examples 8, 12, 17, 22, and 23 of ]-1-butanone have even better sensitivities.

In addition, Examples 13 to 18, Example 22, Example 25, and Example 26 further containing a silane coupling agent (S) were very excellent in adhesiveness and showed high resolution.

In addition, Examples 19 to 21 and 23 further containing polyfunctional thiol (F) were excellent in sensitivity.

Moreover, Example 3, Example 5, Example 25, and Example 26 which further contained an antioxidant (G) or a polymerization inhibitor (H) were excellent in resolution.

When other oxime ester-based photopolymerization initiators were used like Comparative Examples 1 and 2, the sensitivity was good but the pattern shape was poor, and it was not possible to obtain a product that was good in all evaluation items.

In addition, when there is no photopolymerizable compound (C) like Comparative Example 3, the filter segments or the black matrix are poorly formed, and a good one cannot be obtained.

About Example 31~Example 52

<Production method of acrylic resin solution>

[Preparation of acrylic resin solution 1]

(Stage 1: Polymerization of the resin backbone)

Put propylene glycol monomethyl ether acetate into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen introduction tube, and a stirring device in a detachable four-necked flask. (PGMAC), 100 parts of styrene, 29 parts of dicyclopentyl methacrylate, and methacrylic acid were added dropwise through a dropper over 2.5 hours at the same temperature while injecting nitrogen into the container. The polymerization reaction was carried out with a mixture of 57 parts of glycidyl ester and 1.0 part of azobisisobutyronitrile as a catalyst required for the precursor reaction in this stage.

(Stage 2: Reaction in epoxy groups)

Next, the air in the flask was replaced, and 29 parts of acrylic acid, 0.3 parts of tris-dimethylaminomethylphenol, and 0.3 parts of hydroquinone, which were the catalysts required for the precursor reaction in this stage, were added, and the reaction was carried out at 120°C. The reaction was carried out for 5 hours, and a resin solution with a weight average molecular weight (Mw) of about 10,500 was obtained. The added acrylate is bonded to the epoxy terminal of the glycidyl methacrylate structural unit, so no carboxyl group is generated in the resin structure.

(Stage 3: Reaction in hydroxyl group)

Furthermore, 46 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine, which is a catalyst required for the precursor reaction in this stage, were added and reacted at 120° C. for 4 hours. Regarding the added tetrahydrophthalic anhydride, one of the two carboxyl groups generated by cleaving the carboxylic anhydride site is ester-bonded to the hydroxyl group in the resin structure, and the other generates a carboxyl terminal.

(Phase 4: Adjustment of non-volatile components)

Propylene glycol monomethyl ether acetate was added so that the non-volatile content would be 20% by weight to obtain an acrylic resin solution. The weight average molecular weight (Mw) is 11500, and the acid value is 103 mgKOH/g.

[Preparation of acrylic resin solution 2]

Put 196 parts of cyclohexanone into a reaction vessel equipped with a thermometer, cooling tube, nitrogen introduction tube, dropper and stirring device in a detachable four-neck flask, and heat it to 80°C. After replacing the nitrogen in the reaction vessel , add 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and methacrylic acid (3-ethyl-3-oxaheterocycle) through a dropper over 2 hours. A mixture of 20.7 parts of butyl)methyl ester and 1.1 parts of 2,2'-azobisisobutyronitrile. After the dropwise addition was completed, the reaction was continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene methoxyacetate was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. ester to prepare acrylic resin solution 2. The weight average molecular weight (Mw) is 24,000.

<Method for producing a resin having a cationic group in a side chain>

(Resin 1 having a cationic group in the side chain)

Put 67.3 parts of methyl ethyl ketone into a four-neck detachable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and heat it to 75°C under a nitrogen stream. In addition, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, and 2,2'- 6.5 parts of azobis (2,4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone were evenly poured into a dropping funnel and installed in a four-neck detachable flask, and added dropwise over 2 hours. . Two hours after the completion of the dropwise addition, it was confirmed from the solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50°C. into it 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50° C. for 2 hours, then heated to 80° C. over 1 hour, and further allowed to react for 2 hours. In this way, resin 1 having an ammonium group and a cationic group in the side chain was obtained as a resin component of 47% by weight. The obtained resin had an ammonium salt value of 34 mgKOH/g.

(Resin 2 having a cationic group in the side chain)

In the production of the resin 1 having a cationic group in the side chain, except that the raw materials were changed to the composition shown in Table 7, the same procedure as the production of the resin 1 having a cationic group was used to obtain a resin having a cationic group. Resin 2.

<Manufacturing method of dye>

(Dye 1)

Dye 1, which is a salt-forming compound containing C.I. Acid Red 289 and resin 1 having a cationic group in the side chain, was produced in the following procedure.

30 parts of the resin 1 having a cationic group in the side chain was added to 2000 parts of water in terms of solid content, and the mixture was thoroughly stirred and mixed, and then heated to 60°C. On the other hand, 10 parts of C.I. Acid Red 289 was dissolved in 90 parts of water. aqueous solution, and add it dropwise in small amounts to the resin solution just now. After the dropwise addition, the mixture was stirred at 60° C. for 120 minutes to fully proceed with the reaction. To confirm the end point of the reaction, the reaction liquid was dropped onto the filter paper, and the point where the penetration disappeared was regarded as the end point, and it was judged that a salt-forming compound was obtained. Allow to cool to room temperature while stirring, then perform suction filtration. After washing with water, use a dryer to remove water and dry the salt-forming compound remaining on the filter paper, thereby obtaining 32 parts of C.I. Acid Red 289 with cationic side chains. The salt-forming compound of the base resin 1 is dye 1. At this time, the content of the effective pigment component derived from C.I. acid red 289 in dye 1 was 27% by weight.

(Dye 2)

In the production of the dye 1, C.I. acid red was obtained in the same procedure as the production of the dye 1, except that the resin 1 having a cationic group in the side chain was changed to the resin 2 having a cationic group in the side chain. 289 is dye 2 which is a salt-forming compound of resin 2 having a cationic group in its side chain.

<Production method of dispersant>

(Synthesis of dispersant (X-1))

Put 50 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, and methacrylic acid (3-ethyl-3-oxetane) into a reaction vessel equipped with a gas introduction pipe, a thermometer, a condenser, and a stirrer. 20 parts of methyl ester and 45.4 parts of PGMAc, and replaced with nitrogen. The reaction vessel was heated to 70°C, 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 parts of Azobisisobutyronitrile (AIBN) was added, and the reaction was carried out for 12 hours. It was confirmed by solid content measurement that 95% had reacted. Next, add 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and as a catalyst 0.20 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene (DBU), and react at 120°C 7 hours. By measuring the acid value, it was confirmed that more than 98% of the acid anhydride was half-esterified and the reaction was completed. PGMAc was added and the non-volatile content was adjusted to 50% to obtain a dispersant (X-1) with an acid value of 43 and a weight average molecular weight of 9000.

<Production method of pigment dispersion>

[Preparation of red pigment dispersion P-R1]

The mixture of the following composition was stirred and mixed evenly, and then dispersed for 5 hours using an Eiger Mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 1 mm. , filtered with a 5 μm filter to prepare red pigment dispersion P-R1.

[Chemistry 20]

[Preparation of red pigment dispersion P-R2]

The mixture of the following composition was stirred and mixed evenly, and then dispersed for 5 hours using an Eiger Mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 1 mm. , filtered with a 5 μm filter to prepare red pigment dispersion P-R2.

[Preparation of green pigment dispersion P-G1]

A green pigment dispersion P-G1 was prepared in the same manner as the red pigment dispersion using a mixture of the following composition.

[Preparation of green pigment dispersion P-G2]

A green pigment dispersion P-G2 was prepared in the same manner as the red pigment dispersion using a mixture of the following composition.

[Preparation of blue pigment dispersion P-B1]

Using a mixture of the following composition, blue pigment dispersion P-B1 was prepared in the same manner as the red pigment dispersion.

[Preparation of blue pigment dispersion P-B2]

Using a mixture of the following composition, blue pigment dispersion P-B2 was prepared in the same manner as the red pigment dispersion.

[Preparation of blue pigment dispersion P-B3]

Using a mixture of the following composition, blue pigment dispersion P-B3 was prepared in the same manner as the red pigment dispersion.

[Preparation of black pigment dispersion P-BK]

Using a mixture of the following composition, black pigment dispersion P-BK was prepared in the same manner as the red pigment dispersion.

(Preparation of photosensitive coloring composition)

Each material was mixed and stirred at the formula ratio shown in Tables 8 to 11, and filtered with a 1 μm filter to obtain photosensitive coloring compositions of each color.

The symbols in Tables 8 to 11 have the same meanings as those used in Tables 1 to 3.

Regarding the pattern formation, sensitivity evaluation, linearity evaluation, pattern shape evaluation, analytical evaluation, development resistance evaluation, and chemical resistance evaluation of the obtained photosensitive colored composition, the evaluation is as described above. Examples 1 to 30 were carried out in the same manner. Heat resistance evaluation was performed by the following method.

[Heat resistance evaluation]

The chromaticity ([L *(1), a*(1), b*(1)]). Furthermore, as a heat resistance test, the sample was heated at 230° C. for 1 hour, and the chromaticity ([L*(2), a*(2), b*(2)]) under C light source was measured. According to the following formula Find the color difference △Eab*.

△Eab*=√((L*(2)-L*(1))2+(a*(2)-a*(1))2+(b*(2)-b*(1))2 )

The evaluation levels are as follows.

◎: △Eab* is less than 5.0

○: △Eab* is 5.0 or more and less than 10.0

×: △Eab* is 10.0 or more

The evaluation results are shown in Tables 12 to 14.

As shown in Tables 12 to 14, the filter segments and black matrices formed using the photosensitive coloring compositions of Examples 31 to 52 have good sensitivity, linearity, resolution and heat resistance. The present application The pattern shapes of Examples 37 to 40, Example 42, Example 45, Example 46, and Example 49 in which the photopolymerization initiator (A) was used in combination with other photopolymerization initiator (Y) showed better Excellent characteristics. The other photopolymerization initiator (Y) is 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl Example 38, Example 42, and Example 46 of ]-1-butanone have even better sensitivities.

In addition, Examples 43 to 46 further containing polyfunctional thiol (F) have excellent sensitivities.

Moreover, Example 33, Example 35, Example 47, and Example 48 which further contained an antioxidant (G) or a polymerization inhibitor (H) were excellent in resolution.

When using other oxime ester photopolymerization initiators as in Comparative Examples 4 and 5 In this case, the sensitivity is good but the pattern shape is poor, and all evaluation items are not good.

In addition, when there is no photopolymerizable compound (C) like Comparative Example 6, the filter segments or the black matrix are poorly formed, and a good one cannot be obtained.

Moreover, like Comparative Example 7 and Comparative Example 8, when none of the colorant, resin, and dispersant contains an oxetanyl group, the heat resistance is poor.

Claims (6)

A photosensitive coloring composition characterized by containing: a photopolymerization initiator (A) represented by the following general formula (1), a resin (B), a photopolymerizable compound (C), a colorant (D), and other photopolymerization initiators (Y);

In the general formula (1), R ₁ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, an unsubstituted aryl group, a substituted or Unsubstituted aryloxy, substituted or unsubstituted heterocyclyl, substituted or unsubstituted heterocycloxy, substituted or unsubstituted alkylmercapto, substituted or unsubstituted aryl mercapto group, substituted or unsubstituted acyl group, or substituted or unsubstituted amine group, R ₂ , R ₃ , R ₄ respectively independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, Substituted or unsubstituted heterocyclyl, substituted or unsubstituted heterocycloxy, substituted or unsubstituted alkylmercapto, substituted or unsubstituted arylmercapto, substituted or unsubstituted A substituted acyl group, or a substituted or unsubstituted amine group, and the other photopolymerization initiator (Y) includes a compound selected from the group consisting of an acetophenone compound, a phosphine compound, and an imidazole compound. At least one compound, and the content of the other photopolymerization initiator (Y) is 1 to 3000 parts by weight relative to 100 parts by weight of the photopolymerization initiator (A). The photosensitive coloring composition according to claim 1, which further contains a dispersant and is selected from the group consisting of the resin (B), the colorant (D) and the dispersant. At least one of has an oxetanyl group. The photosensitive coloring composition according to claim 2, wherein the dispersant has an oxetane group, the dispersant contains a dispersant (X), and the dispersant (X) has : The polyester part X1' is made by reacting the acid anhydride group in one or more acid anhydrides (b) selected from the group consisting of tetracarboxylic dianhydride (b1) and tricarboxylic anhydride (b2) and the hydroxyl group in the hydroxyl-containing compound (a). and has a carboxyl group; and the vinyl polymer part X2' is formed by free radical polymerization of the ethylenically unsaturated monomer (c), and the vinyl polymer part X2' has an oxetanyl group. The photosensitive coloring composition according to any one of claims 1 to 3, further comprising a silane coupling agent (S). The photosensitive coloring composition according to any one of claims 1 to 3, further containing a polyfunctional thiol (F). A color filter characterized by having filter segments or a black matrix formed of the photosensitive coloring composition as described in any one of items 1 to 5 of the patent application on a transparent substrate.