WO2018025806A1 - Photosensitive coloring composition and color filter - Google Patents

Abstract

Provided are a photosensitive coloring composition which has high sensitivity, as well as excellent linearity, pattern shape, resolution, developing resistance, and chemical resistance and which can further have excellent heat resistance, even if the pigment content is high or film thickness is large, and a color filter using the photosensitive coloring composition. The photosensitive coloring composition may comprise 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 the resin (B), the coloring agent (D), and the dispersant may have an oxetane group.

Description

Photosensitive coloring composition and color filter

The present invention relates to a photosensitive coloring composition, and particularly to a liquid crystal display device, a color display device using a white light emitting organic EL (electroluminescence) element (hereinafter sometimes referred to as “organic EL element”), and a solid-state imaging element. The present invention relates to a highly sensitive photosensitive coloring composition useful for forming each color filter segment such as red, green, and blue and a black matrix in the color filter used. White means a broad concept including pseudo white. The present invention also relates to a color filter formed using the photosensitive coloring composition.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundred microns, and are regularly arranged in a predetermined arrangement for each hue.
Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
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 applied to a transparent substrate such as glass, the solvent is removed by drying, and then pattern exposure of one filter color is performed. Next, the unexposed area is removed in the development process to form a pattern for the first color, and after processing such as heating as necessary, the same operation is sequentially repeated for all filter colors to produce a color filter. can do.

In recent years, color liquid crystal display devices have formed a large market for liquid crystal color televisions, car navigation and liquid crystal display integrated laptops, and monitors and televisions for desktop computers that take advantage of energy and space saving features. As it has begun to spread. Although attention is paid to a display device that replaces a conventional CRT, the color reproduction characteristic of a liquid crystal display device is inferior to that of a CRT at present.
Therefore, there is an increasing demand for high color reproducibility in color filters in which filter segments for each color are arranged.

In order to improve contrast, a black matrix is generally arranged between the filter segments of each color of the color filter. However, the material for forming this black matrix has recently become an environmental problem, low reflection, and low cost. In view of the above, attention is focused on a resin black matrix in which a light-shielding pigment is dispersed in a resin instead of a metal chromium black matrix. However, the resin black matrix has a problem that the light shielding property (optical density) is lower than that of the metal chromium black matrix.

In order to improve the color reproduction characteristics of the color filter and to improve the light blocking property of the black matrix, it is necessary to increase the pigment content in the photosensitive coloring composition or to increase the film thickness. However, in the method of increasing the pigment content, problems such as sensitivity reduction, developability, and resolution deteriorate. In the method of increasing the film thickness, there is a problem that the exposure light does not reach the bottom of the film and the pattern shape becomes defective.
In order to solve such problems, it is necessary to increase the sensitivity of the photosensitive coloring composition. In general, (1) provision of a reactive double bond of the resin, (2) photopolymerization initiator, Selection or increase of the sensitizer, (3) selection or increase of the monomer, etc. are carried out. Examples thereof include Patent Documents 1 and 2.

JP 2001-264530 A JP 2003-156842 A

However, improvement in sensitivity is limited only by the provision of a double bond of the resin and the selection of a photopolymerization initiator, a sensitizer, and a monomer. In particular, when the amount of the photopolymerization initiator is increased, coloring due to a color unique to the photopolymerization initiator, a decrease in heat resistance, a decrease in light transmittance, a decrease in resolution, and the like occur. Further, when the amount of the monomer is increased, problems such as tackiness occur.
Therefore, the embodiment of the present invention has high sensitivity, excellent linearity, pattern shape, resolution, development resistance, chemical resistance, and excellent heat resistance even when the pigment content is high or the film thickness is large. An object is to provide a photosensitive coloring composition and a color filter using the same.

The photosensitive coloring composition according to an embodiment of the present invention is highly sensitive and has the following general formula (1) in order to obtain excellent linearity, pattern shape, resolution, development resistance, and chemical resistance. The photopolymerization initiator represented is used.
That is, the photosensitive coloring composition by one Embodiment of this invention contains the photoinitiator (A) represented by following General formula (1), resin (B), and photopolymerizable compound (C). And a coloring agent (D).
In order to obtain a photosensitive coloring composition according to another embodiment of the present invention with high sensitivity and excellent linearity, pattern shape, resolution, development resistance, chemical resistance, and heat resistance, the following general formula: The photopolymerization initiator represented by (1) is used, and at least one selected from a resin, a colorant and a dispersant has an oxetane group.
That is, the photosensitive coloring composition by one Embodiment of this invention contains the photoinitiator (A) represented by following General formula (1), resin (B), and photopolymerizable compound (C). And at least one selected from the resin (B), the colorant (D), and the dispersant is a photosensitive coloring composition having an oxetane group.

General formula (1)

[In General Formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted Alternatively, it represents an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. ]

In one embodiment of the present invention, the dispersant has an oxetane group,
The dispersant is
An acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2) is reacted with a hydroxyl group in the hydroxyl group-containing compound (a). Polyester part X1 ′ having a carboxyl group;
A dispersant (X) having a vinyl polymer portion X2 ′ formed by radical polymerization of an ethylenically unsaturated monomer (c),
In addition, the present invention relates to the photosensitive coloring composition, wherein the portion X2 ′ has an oxetane group.

Further, one embodiment of the present invention relates to the photosensitive coloring composition, further comprising another photopolymerization initiator (Y).

Another embodiment of the present invention is characterized in that the other photopolymerization initiator (Y) includes at least one compound selected from the group consisting of an acetophenone compound, a phosphine compound, and an imidazole compound. The present invention relates to the photosensitive coloring composition.

Further, one embodiment of the present invention relates to the photosensitive coloring composition, further comprising a silane coupling agent (S).

Moreover, one embodiment of the present invention relates to the photosensitive coloring composition, further comprising a polyfunctional thiol (F).

Also, an embodiment of the present invention relates to a color filter comprising a filter segment or a black matrix formed from the photosensitive coloring composition 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, so that even if the pigment content is high or the film thickness of each color filter segment and black matrix is large, Each color filter segment and black matrix pattern can be formed with high sensitivity and excellent linearity, pattern shape, resolution, development resistance, chemical resistance, and excellent heat resistance.
Therefore, a high quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

First, the photosensitive coloring composition in this invention is demonstrated concretely.
The photosensitive coloring composition by one Embodiment of this invention contains the photoinitiator (A) represented by General formula (1), and resin (B), a photopolymerizable compound (C), and coloring Contains agent (D).

The photosensitive coloring composition by another embodiment of this invention contains the photoinitiator (A) represented by General formula (1), resin (B), photopolymerizable compound (C), The colorant (D) and the dispersant are contained, and at least one selected from the resin (B), the colorant (D) and the dispersant has an oxetane group.

The photopolymerization initiator (A) containing the compound represented by the general formula (1) has high sensitivity, and a coating film having a particularly high residual film ratio is obtained. A colored composition is obtained. By using the photosensitive coloring composition containing the photopolymerization initiator, it is possible to form excellent linearity, pattern shape, resolution, development resistance, chemical resistance filter segment and black matrix.
Further, a better pattern shape can be obtained by using other initiators together.

In addition, since at least one selected from the resin (B), the colorant (D) and the dispersant has an oxetane group, the heat resistance after curing is excellent, and thus a photosensitive coloring composition containing the structure is obtained. By using it, an excellent heat-resistant filter segment and black matrix can be formed.

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

General formula (1)

R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted An alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, It represents a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.

The hydrogen atom of the substituent in R ₁ to R ₄ described above may be further substituted with another substituent.

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, aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyl Alkylamino groups such as mino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, tert-butyl group Alkyl groups such as dodecyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, aryl groups such as benzofuranyl groups, heterocyclic groups such as furyl groups, thienyl groups, etc. Others, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, Phosphono group, trimethylammonyl group, dimethylsulfur group Niumiru group, triphenyl phenacyl phosphonium Niu mill group, and the like.

As the most preferable structure of the photopolymerization initiator (A), compounds represented by the following formulas (2) and (3) may be mentioned.
Formula (2)

Formula (3)

The photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention is an oxime ester photopolymerization initiator. Oxime ester-based photopolymerization initiators are thought to absorb the ultraviolet rays and decompose the oxime ester moiety to generate iminyl radicals and alkyloxy radicals, and the radicals of the active species generated by further decomposition cause the reaction. However, the photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention has a structure represented by the general formula (1), so that the decomposition efficiency by ultraviolet irradiation is very high, A pattern can be formed with a small exposure amount.
The reason why the photopolymerization initiator (A) of the present invention can function with higher sensitivity than the conventional initiator is considered as two possible reasons, but the details are not clear.

The first reason is that the photopolymerization initiator (A) of the present invention has extremely good ultraviolet absorption performance due to the structure represented by the general formula (1). It can absorb well. Furthermore, it is conceivable that the obtained energy is efficiently used for the decomposition of the oxime ester moiety, so that the decomposition by the energy beam irradiation is fast and a large amount of radicals can be generated instantaneously.

The second reason is that the photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1), in which decomposition of an iminyl radical generated by absorbing ultraviolet rays into an active species radical occurs. It can be considered that it is very fast. If the iminyl radical to be produced is metastable, the decomposition is slowed down and the amount of active radicals produced is reduced, but this is greatly affected by the chemical structure of the UV-absorbing moiety. The photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1), so that iminyl radicals generated by decomposition by light irradiation are decomposed very quickly, and a large amount of radicals are generated. It is thought that it has brought.
Moreover, since the photoinitiator (A) of this invention is decomposition | disassembly of an iminyl radical is very quick as mentioned above, it is thought that recombination is suppressed. When the number of recombination is large, the active species generated by the decomposition is reduced, so that the function as a radical polymerization initiator is lowered.

The photopolymerization initiator (A) represented by the general formula (1) is preferably 1 to 50 parts by weight, particularly preferably 1 to 100 parts by weight of the colorant (D) in the photosensitive coloring composition. It can be used in an amount of up to 30 parts by weight.

<Other photopolymerization initiator (Y)>
In the photosensitive coloring composition according to the embodiment of the present invention, it is further preferable to use other photopolymerization initiator (Y) together with the photopolymerization initiator (A) represented by the general formula (1). This is preferable because a pattern shape can be obtained.
Other photopolymerization initiators (Y) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy- 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Acetophenone compounds such as butanone, benzoin, benzoin methyl ether, benzoin ethyl ether Benzoin compounds such as benzoin isopropyl ether and benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3 , 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and other benzophenone compounds, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4 -Thioxanthone compounds such as diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-tri Gin, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloro Methyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine compounds such as 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine and the like, bis (2,4 , 6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and other phosphine compounds, 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'-bis (o-chlorophenyl) ) -4,4 ′, 5,5′-tetra (p-methylphenyl) biimidazole, imidazole compounds, 9,10-phenanthrenequinone, Nfakinon, quinone-based compounds such as ethyl anthraquinone, borate compounds, carbazole-based compounds, titanocene-based compounds can be used.

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

These other photopolymerization initiators (Y) can be used alone or in combination of two or more at any ratio as required. 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, with respect to 100 parts by weight of the colorant (D) in the photosensitive coloring composition. .
Further, it can be used in an amount of 1 to 3000 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (A). In order to obtain a better pattern shape, an amount of 5 to 2000 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (A) is preferable.

<Sensitizer (E)>
Further, the photosensitive coloring composition according to the embodiment of the present invention can contain a sensitizer (E). The content of the sensitizer (E) can be used in an amount of 1 to 200 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (A) in the photosensitive coloring composition.

Sensitizers (E) include chalcone derivatives and unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin Conductor, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphylline derivative, annulene derivative, spiropyran derivative, Examples include spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler ketone derivatives, and the like.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

Among the sensitizers (E), examples of the sensitizer capable of particularly suitably sensitizing the compound represented by the general formula (1) include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like can be used.
The sensitizer (E) may contain two or more sensitizers in any ratio.

<Resin (B)>
The resin (B) contained in the photosensitive coloring composition according to the embodiment of the present invention has a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. It is. 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 the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like.

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.

Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting with an acid can be used. A linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products can also be used.

The resin having an oxetane group can be achieved, for example, by copolymerizing an ethylenically unsaturated monomer having an oxetane group.
Examples of the ethylenically unsaturated monomer having an oxetane group include (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, (3-butyl-3 -Oxetanyl) methyl (meth) acrylate, (3-hexyltyl-3-oxetanyl) methyl (meth) acrylate, and the like.
Examples of commercially available products include ETERNACOLL OXMA (manufactured by Ube Industries), OXE-10, OXE-30 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.
When the resin has an oxetane group, the colored composition containing the resin has excellent heat resistance after being cured.

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, for example, methyl (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) ) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexa Diol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate , Ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate Glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N Vinylformamide and acrylonitrile. These can be used alone or in admixture of two or more.

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) and the weight [M] of the photopolymerizable compound (C) is 0.01-3. 00 is preferable, and 0.15-2.00 is more preferable.
Furthermore, when a photosensitive coloring composition contains a sensitizer (E) and other photoinitiators (Y), a photoinitiator (A), a sensitizer (E), and other photopolymerization The ratio [I _b / M] of the total weight (I _b ) of the initiator (Y) and the weight [M] of the photopolymerizable compound (C) is preferably 0.01 to 3.00, 0 More preferably, it is 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. 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.

<Colorant (D)>
As the colorant (D) contained in the photosensitive coloring composition according to the embodiment of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance are preferable, and organic pigments are usually used. Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition by embodiment of this invention is shown with a color index number.
Further, the colorant (D) can contain a dye within a range that does not lower the heat resistance.

The colorant having an oxetane group can be achieved, for example, by using an ethylenically unsaturated monomer containing an oxetane structure in a resin constituting a salt-forming compound containing a dye. By having an oxetane group, the coloring composition containing the coloring agent is excellent in heat resistance after being cured.

Examples of red pigments include C.I. 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, 17 , 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, and the like. Among these, azo pigments, diketopyrrolopyrrole-based, anthraquinone-based, quinophthalone-based, isoindoline-based, perinone-based, perylene-based, and benzimidazolone-based pigments are exemplified from the viewpoint of brightness and coloring power. Specifically, C.I. I. Pigment Red 176, 177, 179, 254, 242 and a naphthol azo pigment represented by the following general formula (4) are preferable.

General formula (4)

[In General Formula (4), A represents a hydrogen atom, a benzimidazolone group, an optionally substituted phenyl group or an optionally substituted heterocyclic group. 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 each independently represents 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 is represented. R ⁷ to R ¹³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
However, it is excluded when R ⁴ is —NHCOR ¹² and A, R ² , R ³ , R ⁵ , and R ⁶ are hydrogen atoms and R ¹ is a halogen atom. ]

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6. In addition, aluminum phthalocyanine pigments described in JP-A No. 2004-333817, Japanese Patent No. 4893859 and the like can also be used, and the invention is not particularly limited thereto.

Examples of green pigments include C.I. 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 Can be mentioned. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Green 7, 36, 58, 59, 62, and 63. In addition, zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like can be used, and the invention is not particularly limited thereto.

Examples of yellow pigments include C.I. 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, 17 174, 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 and the like. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment yellow 138, 139, 150, 185, 231. In addition, quinophthalone pigments described in Japanese Patent No. 4999326 can be used, and the invention is not particularly limited thereto.

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

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

Examples of the black photosensitive coloring composition for forming the black matrix include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C.I. I. Pigment Black 1, 6, 7, 12, 20, 31, etc. can be used. For the black photosensitive coloring composition, a mixture of a red pigment, a blue pigment, and a green pigment can also be used. As the black pigment, carbon black is preferable from the viewpoint of price and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together in a black photosensitive coloring composition.

Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments can be used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while balancing the saturation and lightness.

"dye"
The coloring composition by embodiment of this invention can also use dye as a coloring agent. 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 and the like can be used. Moreover, it may be in the form of lake pigments obtained by rake-forming these derivatives or dyes.

Furthermore, in the case of an acid dye having an acid group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, an inorganic salt of an acid dye, an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, use a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or salt formation using a resin component having these functional groups, or use it as a salt-forming compound after sulfonamidation. Therefore, it is possible to obtain a colored composition having excellent fastness, which is preferable.
A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of excellent fastness. More preferably, the compound having an onium base is a resin having a cationic group in the side chain.

In the case of a basic dye form, it can be used after being salted using an organic acid, perchloric acid or a metal salt thereof. A salt forming compound of a basic dye is preferable because of its excellent resistance and compatibility with a pigment, and further, a basic dye and an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound that is a counter component that works as a counter ion It is more preferable to use a salt-forming compound obtained by salting a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acidic dye. Is.

Moreover, when it has a polymerizable unsaturated group in a pigment | dye frame | skeleton, it can be set as the dye excellent in tolerance, and it is preferable.
Moreover, when a dye has an oxetane group, the coloring composition containing this dye is excellent in heat resistance after hardening.

In one embodiment, the chemical structure of the dye includes, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, Anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azines Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes It dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and the like dye structure derived from a dye selected from those metal complex dyes.

Among these pigment structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium from the viewpoint of color characteristics such as hue, color separation, and color unevenness Preferred are dye structures derived from dyes selected from dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, phthalocyanine A pigment structure derived from a pigment selected from the system dyes is more preferable. For specific pigment compounds that can form pigment structures, see "New Edition Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyer's and Colorists), "Dye Handbook" (Okawara et al.) Ed; Kodansha, 1986).

Examples of the dye in another embodiment include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, methine dyes, diarylmethane dyes, triarylmethane dyes, Xanthene dye, thiazine dye, cationic dye, cyanine dye, nitro dye, quinoline dye, naphthoquinone dye, oxazine dye, perylene dye, diketopyrrolopyrrole dye, quinacridone dye, ansanthrone Examples include, but are not limited to, dyes, isoindolinone dyes, isoindoline dyes, indanthrone dyes, coumarin dyes, quinacridone dyes, pyranthrone dyes, flavanthrone dyes, and perinone dyes.

Further examples of organic dyes that can be used in another embodiment include triarylmethanes, xanthenes, and anthraquinones, among which xanthenes are preferably used.

[Xanthene dyes]
The xanthene dyes that can be preferably used are red and purple, and preferably have any form of oil-soluble dyes, acid dyes, direct dyes, and basic dyes. In addition, a lake pigment in which these dyes are raked may be used.
Among these, it is preferable to use a xanthene oil-soluble dye or a xanthene acid dye because of excellent hue.

Examples of red and purple colors include C.I. I. Solvent Red, C.I. I. Oil-soluble dyes such as solvent violet, C.I. I. Basic Red, C.I. I. Basic dyes such as basic violet, C.I. I. Acid Red, C.I. I. Acid dyes such as Acid Violet, C.I. I. Direct Red, C.I. I. Examples include those belonging to direct dyes such as direct violet.
Here, the direct dye has a sulfonic acid group (—SO ₃ H, —SO ₃ Na) in the structure, and in the present disclosure, the direct dye is regarded as an acid dye.

Moreover, it is preferable that the xanthene-based basic dye is used after being salified with an organic acid or perchloric acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used. Of these, naphthalenesulfonic acid such as tobias acid and perchloric acid are preferably used in terms of resistance.

In addition, xanthene-based acidic dyes are used as salt-forming compounds by chlorination using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., or resin components having these functional groups. In view of resistance, it is preferable to use it as a sulfonamide compound after sulfonamidation.

Salt forming compounds of xanthene acid dyes and / or sulfonic acid amide compounds of xanthene acid dyes are preferred because of their excellent hue and resistance, and quaternary ammonium which is a counter component that functions as a counter ion. It is more preferable to use a compound prepared by using a salt compound and a sulfonic acid amide compound obtained by sulfonamidating a xanthene acid dye.

Of the xanthene dyes, rhodamine dyes are preferred because they are excellent in color developability and resistance.

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

[Xanthene oil-soluble dye]
Xanthene oil-soluble dyes include C.I. I. Solvent Red 35, C.I. I. Solvent Red 36, C.I. I. Solvent Red 42, C.I. I. Solvent Red 43, C.I. I. Solvent Red 44, C.I. I. Solvent Red 45, C.I. I. Solvent Red 46, C.I. I. Solvent Red 47, C.I. I. Solvent Red 48, C.I. I. Solvent Red 49, C.I. I. Solvent Red 72, C.I. I. Solven Red 73, C.I. I. Solvent Red 109, C.I. I. Solvent Red 140, C.I. I. Solvent Red 141, C.I. I. Solvent Red 237, C.I. I. Solvent Red 246, C.I. I. Solvent Violet 2, C.I. I. Solvent violet 10 and the like.
Among them, C.I., which is a rhodamine-based oil-soluble dye having high color developability. I. Solvent Red 35, C.I. I. Solvent Red 36, C.I. I. Solvent Red 49, C.I. I. Solvent Red 109, C.I. I. Solvent Red 237, C.I. I. Solvent Red 246, C.I. I. Solvent violet 2 is more preferable.

[Xanthene basic dye]
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Examples thereof include basic violet 10 (rhodamine B). Among these, C.I. I. Basic Red 1, C.I. I. It is preferable to use basic violet 10.

[Xanthene acid dyes]
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

The acid dye (not limited to xanthene) is preferably a salt-forming compound of an acid dye and a nitrogen-containing compound, such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, or the like. It is preferable to form a salt using a resin component having these functional groups to obtain a salt-forming compound of an acidic dye because high heat resistance, light resistance, and solvent resistance can be imparted. Acid dyes can impart high heat resistance, light resistance, and solvent resistance by sulfonamidation.
Further, it may be a salt-forming compound of an acid dye and a compound having an onium base, and among them, the compound having an onium base is a resin having a cationic group in the side chain, thereby reducing the brightness and resistance. It can be set as the outstanding coloring composition.

Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetra Examples include aliphatic unsaturated primary amines such as decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, cured tallow alkylamine, allylamine, aniline, and benzylamine. .

Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl. Amine, di-cured tallow alkylamine, distearylamine, etc.

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

(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 a salt-forming compound (a) comprising an acid dye and a quaternary ammonium salt compound.
The quaternary ammonium salt compound as the counter component of the acid dye will be described. A quaternary ammonium salt compound becomes an acid dye counter by having an amino group.

The preferred form of the quaternary ammonium salt compound that is the counter component of the salt-forming compound (a) is colorless or white. Here, colorless or white means 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 entire wavelength region of 400 to 700 nm in the visible light region. Is. That is, it is preferably one that does not inhibit the color development of the dye component and does not cause a color change.

The molecular weight of the counter portion, which is the cation component of the quaternary ammonium salt compound, is preferably in the range of 190 to 900. Here, the cation moiety corresponds to a (NR ₁ R ₂ R ₃ R ₄ ) ⁺ moiety in the following general formula (3). If the molecular weight is smaller than 190, light resistance and heat resistance may be lowered, and further solubility in a solvent may be lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the color forming component in the molecule is lowered, the color developability is lowered, and the lightness can be lowered. More preferably, the molecular weight of the counter portion is in the range of 240 to 850. Particularly preferred is a molecular weight of the counter portion in the range of 350-800. Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

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

General formula (3)

(In the general formula (5), R ₁ to R ₄ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R ₁ , R ₂ , R ₃ , and R ₄ are present. C number of 5 to 20 .Y ^- represents an inorganic or organic anion).

By setting the number of C of at least two of R ₁ to R ₄ to 5 to 20, the solubility in a solvent becomes good. When the number of alkyl groups having a C number of less than 5 is 3 or more, solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Moreover, when the alkyl group in which the number of C exceeds 20 exists, the color development property of a salt-forming compound (a) will be impaired.

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

The quaternary ammonium salt compounds include tetramethylammonium chloride, tetraethylammonium chloride, monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, tristearylmonomethylammonium chloride, cetyltrimethylammonium chloride, trioctylmethylammonium chloride, dioctyldimethylammonium chloride. , Monolauryltrimethylammonium chloride, dilauryldimethylammonium chloride, trilaurylmethylammonium chloride, triamylbenzylammonium chloride, trihexylbenzylammonium chloride, trioctylbenzylammonium chloride, trilaurylbenzylammonium chloride Chloride, benzyl dimethyl stearyl ammonium chloride, and benzyl dimethyl octyl ammonium chloride, and the like dialkyl (alkyl C14 ~ C18) dimethyl ammonium chloride (hydrogenated tallow) and the like.

Specific quaternary ammonium salt compound products include, for example, Cotamin 24P, Cotamin 86P Conch, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50 manufactured by Lion Corporation, and other products such as Lion Co., Ltd. 80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes, etc., among others, Cotamine D86P (distearyldimethylammonium chloride), Arcard 2HT-75 (dialkyl (alkyl is C14- C18) dimethylammonium 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 ′) comprising an acid dye and a resin having a cationic group in the side chain. The resin having a cationic group in the side chain for obtaining the salt-forming compound (a ′) used in the embodiment of the present invention will be described.
The resin having a cationic group in the side chain for obtaining a salt-forming compound is not particularly limited as long as it has at least one onium base in the side chain, but a suitable onium salt structure is available. From the viewpoint of the above, ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable, and ammonium salts, iodonium salts, and sulfonium salts are preferable in view of storage stability (thermal stability). It is more preferable. More preferred is an ammonium salt.

When preparing a blue coloring composition for a color filter containing a salt-forming compound (a ′) and exhibiting the characteristics as a color filter, the same kind of resin as the binder resin constituting the blue coloring composition for the color filter is used. It is preferable to do. In one embodiment of the present invention, an acrylic resin is preferably used as the binder resin in the color filter coloring composition, and therefore, the resin having a cationic group in the side chain for obtaining the salt-forming compound (a ′) is An acrylic resin is preferred.

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

General formula (5)

[In General Formula (5), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ^{52 ~} R ⁵⁴ each independently represent a hydrogen atom, an optionally substituted alkyl group, an alkenyl group which may be substituted or an optionally substituted aryl group, the R ^{52 ~} R ⁵⁴ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁵ —, and R ⁵⁵ represents an alkylene group. Y ⁻ represents an inorganic or organic anion. ]

Examples of the alkyl group for R ⁵¹ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. 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 and an alkoxyl group.

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

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

Here, examples of the alkyl group in R ⁵² to R ⁵² include straight chain alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n -Tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3) -Tetramethylbutyl etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl and 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, 2-methyl-2-propenyl and the like) and cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). 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 (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and aromatic heterocyclic hydrocarbons. Groups (thienyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (from xanthone) Derived groups) and 9-oxothioxanthenyl (groups derived from thioxanthone) and the like.

When the alkyl group, alkenyl group or aryl group represented by R ⁵² to R ⁵⁴ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

R ⁵² to R ⁵⁴ are preferably an alkyl group which may be substituted from the viewpoint of stability, and more preferably an unsubstituted alkyl group.

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 linking the vinyl moiety and the ammonium base represents an alkylene group, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁵ —, and R ⁵⁵ represents an alkylene group. Of these, —CONH—R ⁵⁵ — and —COO—R ⁵⁵ — are preferred because of polymerizability and availability. 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 component Y ⁻ in the general formula (5) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; Carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

One method for introducing an oxetane group into a resin having a cationic group in the side chain is that the ethylenically unsaturated monomer containing an oxetane structure corresponds to the cationic group represented by the general formula (5). This is a method of copolymerizing with an ethylenically unsaturated monomer.
Examples of the ethylenically unsaturated monomer having an oxetane group include (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, (3-butyl-3 -Oxetanyl) methyl (meth) acrylate, (3-hexyltyl-3-oxetanyl) methyl (meth) acrylate, and the like.
Examples of commercially available products include ETERNACOLL OXMA (manufactured by Ube Industries), OXE-10, OXE-30 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

(Salt formation)
A salt-forming compound of an acid dye and a nitrogen-containing compound or a resin having a cationic group in the side chain can be produced by a conventionally known method. A specific technique is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, a xanthene acid dye may be used, and after the xanthene acid dye is dissolved in water, a quaternary ammonium salt compound may be added and subjected to chlorination while stirring. Here, a structure in which the sulfonic acid group (—SO ₃ H) and sodium sulfonate group (—SO ₃ Na) in the xanthene-based acid dye and the ammonium group (NH ₄ ⁺ ) in the quaternary ammonium salt compound are bonded to each other is formed. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

Further, the salt-forming compound is obtained by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (5) and an acidic dye are dissolved, or represented by the general formula (5). It can be easily obtained by mixing an aqueous solution of a resin having a cationic group in the side chain and an aqueous solution of an acidic dye under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the acidic dye are ionized and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the acidic dye is water-soluble and can be removed by washing or the like. As for the resin having a cationic group in the side chain to be used and the acid dye, only a single type or a plurality of types having different structures may be used.
In addition, with 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 in the same manner as the xanthene dye.

(Sulphonic acid amide compound)
The acidic dye may be a sulfonic acid amide compound obtained by reacting a sulfonic acid amide compound with an anionic dye.
A sulfonic acid amide compound of an acid dye that can be preferably used for an acid dye is obtained by chlorinating an acid dye having —SO ₃ H and —SO ₃ Na by a conventional method to convert —SO ₃ H to —SO ₂ Cl. Compounds can be prepared by reacting with amines having —NH ₂ groups.
Specific examples of amine compounds that can be preferably used in sulfonamidation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropyl. It is preferable to use amine, cyclohexylamine or the like.
An example using a xanthene acid dye is C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 289 was converted to a sulfonyl chloride and reacted with the theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 289.
In addition, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 52 was converted to a sulfonyl chloride and reacted with the theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 52.
Moreover, also in other acidic dyes, a sulfonic acid amide compound can be obtained in the same manner as xanthene dyes.

As the xanthene dyes, JP2010-032999A, JP2011-138094A, JP2011-227313A, JP2011-242752A, JP2012-107192A, JP2013-103A. No. 033194, Japanese Patent Application No. 2011-71888, Japanese Patent Application No. 2013-72263, Japanese Patent Application No. 2013-81209, Japanese Patent Application Laid-Open No. 2014-173064, Japanese Patent Application No. 2013-53028, Japanese Patent Application No. 2013-52186 JP, 2014-196392, JP 2014-196393, JP 2014-201714, JP 2014-201715, JP 2013-050693, JP 2013-178478, Japanese Patent Application Laid-Open No. 2013-203156, country It may be a known technique described in Publication No. 2013/011687 pamphlet, and the like.

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

[Dipyrromethene dye]
The dipyrromethene dye is a dye having a partial structure derived from a dipyrromethene dye as a partial structure of the dye part, and is preferably a dipyrromethene compound, and a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound. A metal complex compound in which the 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”) is preferable.

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

General formula (6)

In general formula (6), R ¹ to R ⁶ each independently represents 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. Represents.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or 2 Valent metal chlorides are included. Examples of the metal or metal compound include ZnCl, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and B, as well as AlCl ₃ , InCl ₃ , and FeCl. ₃ , metal chlorides such as TiCl ₂ , SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, as a metal or a metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, and the like from the viewpoint of stability of the complex, spectral characteristics, heat resistance, light resistance, manufacturing suitability, and the like. Ni, Co, TiO, B, or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO is most preferred.

Examples of such dipyrromethene dyes include JP-A-2008-292970, JP-A-2010-85758, JP-A-2010-84009, Japanese Patent Application No. 2010-43530, JP-A-2013-080010, Known techniques described in Japanese Unexamined Patent Publication No. 2013-210596 and International Publication No. 2013/141156 can be used.

[Triphenylmethane dye]
Examples of the triphenylmethane dye skeleton include a diaminotriphenylmethane dye skeleton, a triaminotriphenylmethane dye skeleton, and a rosic acid dye skeleton having an OH group.
Triaminotriphenylmethane-based dye skeletons are preferable in that they are excellent in color tone and more excellent in fastness to sunlight than others. Among them, a diphenylnaphthylmethane dye skeleton that is a basic dye is particularly preferable.

[Triphenylmethane basic dye]
The triphenylmethane-based basic dye develops color when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation.
Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, a triaminoarylmethane-based basic dye is preferable in terms of good blue, red and green coloring.
a) Diaminotriphenylmethane basic dye b) Triaminotriphenylmethane basic dye c) Rosolic acid basic dye having OH group Triaminotriphenylmethane basic dye, diaminotriphenylmethane basic dye The dye has a clear color tone and is preferable because it is more excellent in fastness to sunlight than other dyes.

Since the blue triphenylmethane basic dye has a spectral characteristic having a high transmittance at 400 to 440 nm, it can have a high brightness particularly when used for forming a blue filter segment. This is preferable because it is possible.

Specific examples of triphenylmethane basic dyes include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Examples include Basic Green 1 (Brilliant Green GX) and 4 (Malachite Green).
Above all, from the point of brightness, C.I. I. It is preferable to use Basic Blue 7.

In the case of a triphenyl basic dye, it can be used after salt formation using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because of its resistance and excellent compatibility with pigments, and further, a basic dye and organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus, which are counter components that function as counter ions. It is possible to use a salt-forming compound obtained by salting an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye. It is more preferable.

Specifically, organic acids such as heteropoly acids, organic sulfonic acids such as aliphatic sulfonic acids and aromatic sulfonic acids, organic sulfuric acids such as aliphatic sulfuric acids and aromatic sulfuric acids, organic carboxylic acids such as aromatic carboxylic acids and fatty acids, Or it has the form of an acid dye. Alternatively, a metal salt thereof may be used. A salt-forming compound with a resin having an acid group is also preferable.

(Salt formation)
These salt forming compounds of a basic dye and an anionic counter can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 2003-215850.
For example, after the triarylmethane basic dye is dissolved in water, an organic sulfonic acid or (sodium organic sulfonate) solution may be added and subjected to chlorination treatment while stirring. Here, a salt-forming compound in which the amino group (—NHC ₂ H ₅ ) portion of the triarylmethane-based basic dye and the sulfonic acid group (—SO ₃ H) portion of the organic sulfonic acid are bonded is obtained.
Here, the organic sulfonic acid can be dissolved in an alkali solution such as sodium hydroxide before the salt-forming treatment and used in the form of sodium sulfonate (—SO ₃ Na). In the present disclosure, the sulfonic acid group (—SO ₃ H) and the functional group (—SO ₃ Na) which is sodium sulfonate may be referred to without distinction.

Examples of such triphenylmethane dyes include JP-A No. 2002-014222, JP-A No. 2003-246935, JP-A No. 2003-246935, JP-A No. 2008-304766, and JP-A No. 2010-256598. Japanese Patent Application No. 2011-200560, Japanese Unexamined Patent Application Publication No. 2011-186043, Japanese Unexamined Patent Application Publication No. 2012-173399, Japanese Unexamined Patent Application Publication No. 2012-233303, Japanese Unexamined Patent Application Publication No. 2012-098522, Japanese Patent Application No. 2012-288970, Known techniques described in Japanese Patent Application No. 2012-200469, Japanese Patent Application Laid-Open No. 2014-196262, International Publication No. 2010/123071, Pamphlet of International Publication No. 2011/162217, Pamphlet of International Publication No. 2013/108591, etc. To use Can.

In one embodiment, the triphenylmethane dye may be C.I. I. Acid Violet 15, C.I. I. Acid Violet 17, C.I. I. Acid Violet 19, C.I. I. Acid Violet 21, C.I. I. Acid Violet 24, C.I. I. Acid Violet 25, C.I. I. Acid Violet 38, C.I. I. Acid Violet 49, C.I. I. Acid Blue 1, C.I. I. Acid Blue 3, C.I. I. Acid Blue 5, C.I. I. Acid Blue 7, C.I. I. Acid Blue 9, C.I. I. Acid Blue 11, C.I. I. Acid Blue 13, C.I. I. Acid Blue 15, C.I. I. Acid Blue 17, C.I. I. Acid Blue 22, C.I. I. Acid Blue 24, C.I. I. Acid Blue 26, C.I. I. Acid Blue 75, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I. I. Acid Blue 100, C.I. I. Basic Blue 81, C.I. I. It is preferable to use Basic Blue 83.

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

[Cyanine dyes]
Any cyanine dye can be used without limitation as long as it is a compound having a dye moiety containing a cyanine skeleton in the molecule.
Examples of cyanine dyes include C.I. 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. I. Basic Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I. I. Basic violet 7, 15, 16, 20, 21, 39, 40, C.I. I. Basic orange 27, 42, 44, 46, C.I. I. Basic blue 62, 63, etc. may be mentioned.
In addition, cyanine dyes described in JP2014-224970A, JP2013-261614A, and the like can also be used.

[Anthraquinone dyes]
An anthraquinone dye is a dye having an anthraquinone skeleton in the molecule.
Examples of the anthraquinone dye include C.I. I. Solvent Yellow 117, 163, 167, 189, C.I. I. Solvent Orange 77, 86, C.I. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C.I. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, C.I. 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. I. Solvent Green 3, 28, 29, 32, 33, C.I. I. Acid Red 80, C.I. I. Acid Green 25, 27, 28, 41, C.I. I. Acid Violet 34, C.I. I. Acid Blue 25, 27, 40, 45, 78, 80, 112, C.I. I. Disperse Yellow 51, C.I. I. Disperse violet 26, 27, C.I. I. Disperse Blue 1, 14, 56, 60, C.I. I. Direct Blue 40, C.I. I. Modern Red 3, 11, C.I. I. Modern Blue 8 etc. are mentioned. Also, anthraquinone dyes described in JP-A-9-291237, WO2003 / 080734, WO2006 / 024617, JP2011-174987, JP2013-53273, and the like are used. It can be used as a known technique. The anthraquinone dye is preferably soluble in an organic solvent, and more preferably a blue, violet or red anthraquinone dye. As an anthraquinone dye, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 45, C.I. I. Acid Blue 80, C.I. I. Solvent Blue 104, and C.I. I. Solvent blue 122 is preferable from the viewpoint of brightness and contrast.

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

In recent years, it is necessary to increase the content of the colorant in the photosensitive coloring composition in order to improve the color reproduction characteristics and reduce the thickness of the color filter.
When used in a color liquid crystal display device, the content of the colorant (D) is preferably 20% by weight or more, more preferably in a solid content of 100% by weight of the photosensitive coloring composition for color filter according to the embodiment of the present invention. If it is 30% by weight, particularly preferably 35% by weight or more, sufficient color reproducibility can be obtained, and the film thickness can be reduced. In addition, when the content 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 appropriate, and sufficient curing coating is achieved. A film can be obtained.
When used in an organic EL display device, the content of the colorant (D) is preferably 100% by weight or more, preferably 40% by weight or more, in the solid content of 100% by weight of the photosensitive coloring composition for color filter according to the embodiment of the present invention. If it is preferably 45% by weight, sufficient color reproducibility can be obtained, and the film thickness can be reduced. Moreover, if it is 60 weight% or less, More preferably, it is 55 weight% or less, content of resin and a photopolymerizable compound which are hardening materials will become appropriate, and sufficient cured coating film can be obtained.

<Dispersant>
In general, a dispersant has a structure of a site that adsorbs to a colorant and a site that has a high affinity for a colorant carrier and a solvent that is a dispersion medium, and the performance of the dispersant is determined by the balance between these two sites. That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the colorant and the affinity to the colorant carrier and the solvent as the dispersion medium are very important. The colorant carrier referred to here is composed of a resin, a precursor thereof, or a mixture thereof obtained by removing a colorant component and a dispersant from a solid content.
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, which are used alone or in combination of two or more. Can do.

The dispersant having an oxetane group can be achieved by the dispersant (X) and other dispersants having this structure. When the dispersant has an oxetane group, the coloring composition containing the dispersant is excellent in heat resistance after being cured.

In addition, the dispersant (X) described below is composed of two parts X1 ′ and X2 ′, and it is impossible to specify and describe how these parts are bonded. This is described by the manufacturing method.

<< Dispersant (X) >>
The dispersant (X) is an acid anhydride group in one or more acid anhydrides (b) selected from the tetracarboxylic acid anhydride (b1) and the tricarboxylic acid anhydride (b2) and the hydroxyl group-containing compound (a). It has the polyester part X1 'which has a carboxyl group which is made to react with a hydroxyl group, and the vinyl polymer part X2' which is obtained by radical polymerization of the ethylenically unsaturated monomer (c).

Here, the polyester portion X1 ′ of the main chain acts as a colorant adsorbing group, and the vinyl polymer portion X2 ′ of the side chain acts as a colorant carrier affinity group, thereby suppressing aggregation of the colorant and excellent stability. Dispersion can be obtained.

The content of the dispersing agent (X) is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 60 parts by weight, and still more preferably 5 to 40 parts by weight with respect to 100 parts by weight of the colorant. When content of dispersing agent (X) exists in this range, it can be excellent in dispersibility and tolerance.

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 be reduced. . The acid value of the obtained dispersant is preferably 5 to 200 mgKOH / g. More preferably, it is 5 to 150 mgKOH / g, and particularly preferably 5 to 100 mgKOH / g. If the acid value is less than 5 mgKOH / g, the ability to adsorb to the colorant may be lowered and there may be a problem in dispersibility. There is a case.

Subsequently, each component of the dispersant (X) will be described.
[Hydroxyl-containing compound (a)]
The hydroxyl group-containing compound is not particularly limited as long as it has a hydroxyl group in the molecule, but is preferably a polyol having two or more hydroxyl groups in the molecule, and in particular, two hydroxyl groups and one in the molecule. It is preferable that it is a compound (a1) which has a thiol group.

[Compound having two hydroxyl groups and one thiol group in the molecule (a1)]
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-ethanediol, 3-mercapto-1, 2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, Examples include 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[Other polyols (a2)]
Examples of other polyols (a2) that can be used include those belonging to the following groups (1) to (7), if only typical ones are exemplified. By using these polyol compounds in combination, it becomes easy to adjust the density of the carboxylic acid group and the ratio of the solvent-dissolving part.

(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) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, or Polyhydric alcohols such as hexanetriol;

(2) Various polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol Kind;

(3) Various polyhydric alcohols as described above, and (cyclic) ether bond-containing compounds such as ethylene oxide, 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 of

(4) Polyester polyols obtained by co-condensation with one or more of the various polyhydric alcohols described above and polycarboxylic acids, wherein the polycarboxylic acids are succinic acid, adipic acid, sebacic acid, Azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid, or 2,5,7-naphthalenetricarboxylic acid Resulting polyols;

(5) A lactone obtained by a polycondensation reaction between one or more of the various polyhydric alcohols described above and various lactones such as ε-caprolactone, δ-valerolactone, or 3-methyl-δ-valerolactone. Lactone-based polyester polyols, or lactone-modified polyester polyols obtained by polycondensation reaction of various polyhydric alcohols, polycarboxylic acids, and various lactones;

(6) Epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids, Epoxy-modified polyester polyols obtained by combining one or more of the polyester polyols during synthesis; or

(7) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound, or hydroxyl group-containing silicon resin And other polymer polyols.

These other polyols (a2) optionally added as shown in (1) to (7) may of course be used alone or in combination of two or more, but the weight average molecular weight is as follows. From the viewpoint of solubility and dispersion stability, it is preferably 40 to 10,000, more preferably 100 to 2,000, and still more preferably 100 to 1,000. When the weight average molecular weight is less than 40, the effect of improving the compatibility and dispersion stability is small, and when the weight average molecular weight is 10,000 or more, the compatibility may be deteriorated.

The number of hydroxyl groups in one molecule of the other polyol (a2) is not particularly limited as long as the desired dispersant can be synthesized, but a diol is preferable. In particular, by reacting with tetracarboxylic dianhydride (b1), carboxyl groups serving as pigment adsorbing groups can be regularly arranged in the main chain, which is advantageous for pigment dispersion. When many polyols having more than two hydroxyl groups are used, the main chain of the polyester may be branched and complicated and bulky, and it may be difficult to obtain a dispersion effect. For the purpose of adjusting the molecular weight of the polyester (X) and adjusting the viscosity of the dispersion, it should be minimized from the viewpoint of design.

[Acid anhydride (b)]
The acid anhydride (b) preferably contains one or more selected from tetracarboxylic anhydride (b1) and tricarboxylic anhydride (b2).
The two anhydride groups of the tetracarboxylic dianhydride (b1) react with the hydroxyl groups of the hydroxyl group-containing compound (a), thereby regularly forming carboxyl groups that serve as pigment adsorption groups on the main chain of the dispersant (X). This is advantageous for pigment dispersion.
When tricarboxylic anhydride (b2) is used, it can react with a hydroxyl group to form an ester bond, leaving a carboxyl group.

In addition, polycarboxylic acid anhydrides other than tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2), dicarboxylic acid anhydrides, and anhydrides of compounds having 5 or more carboxylic acids can be used in combination. .

[Tetracarboxylic acid anhydride (b1)]
As tetracarboxylic dianhydride (b1),
1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo Aliphatic tetracarboxylic dianhydrides such as [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, ethylene glycol Dimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4 , 4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride Anhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4, 4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis ( Triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid)- 4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyl) Phenoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or 3,4-dicarboxy-1,2,3,4 And aromatic tetracarboxylic dianhydrides such as tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

The tetracarboxylic dianhydride is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Since tetracarboxylic dianhydride forms a dispersant having two carboxyl groups in one unit of polyester by reaction with polyol, it is preferable as a constituent of dispersant (X) from the viewpoint of pigment adsorptivity. .

Further, preferably used is an aromatic tetracarboxylic dianhydride from the viewpoint of adsorptivity to a colorant, and more preferably a tetracarboxylic dianhydride having two or more aromatic rings. . Aromatic carboxylic acids have higher pigment adsorption capacity than aliphatic carboxylic acids, and carboxylic acids having two or more aromatic rings are skeletons suitable for pigment adsorption and have high heat resistance.

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

General formula (7):

[In General Formula (7), k is 1 or 2. ]

General formula (8):

[In General Formula (8), Q ₁ represents a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO—, —SO ₂ —, —C (CF ₃ ) ₂ —, General Formula (9) :

Or a group represented by the general formula (10):

It is group represented by these. ]

[Tricarboxylic anhydride (b2)]
Examples of the tricarboxylic acid anhydride (b2) include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride and the like.

Examples of the aromatic tricarboxylic acid include benzene tricarboxylic acid anhydride (1,2,3-benzene tricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzene tricarboxylic acid anhydride], etc.), naphthalene tricarboxylic acid, and the like. Acid anhydrides (1,2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1,2,8-naphthalene tricarboxylic acid anhydride 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, or 3,4,4'-biphe Le sulfonic tricarboxylic acid anhydride and the like. Of these, aromatic tricarboxylic acid anhydrides are preferably used from the viewpoint of adsorptivity to pigments.

The ratio of the acid anhydride group in one or more acid anhydrides (b) selected from the tetracarboxylic acid anhydride (b1) and the tricarboxylic acid anhydride (b2) to the hydroxyl group in the hydroxyl group-containing compound (a) The anhydride group / hydroxyl group is preferably 0.5 to 1.5.
When it is smaller than 0.5 or larger than 1.5, there are many portions that do not react with each other, and the intended dispersant is often not obtained.

[Ethylenically unsaturated monomer (c)]
The dispersant (X) has a vinyl polymer site X2 ′ formed by radical polymerization of the ethylenically unsaturated monomer (c). Examples of the ethylenically unsaturated monomer (c) include an ethylenically unsaturated monomer (c1) having an oxetane group and other ethylenically unsaturated monomers, and a mixture of two or more of these is used. be able to.

[Ethylenically unsaturated monomer having oxetane group (c1)]
By copolymerizing the ethylenically unsaturated monomer (c1) having an oxetane group, the oxetane group can be introduced into the vinyl polymer portion X2 ′.
The content of the ethylenically unsaturated monomer (c1) having an oxetane group is 5 to 70% by weight based on the total (100% by weight) of all the ethylenically unsaturated monomers (c). Preferably, it is 10 to 50% by weight. When the content is 5% by weight or more, the cross-linking property is excellent and the resistance is better. When the content is 70% by weight or less, the stability is excellent.

Examples of the ethylenically unsaturated monomer (c1) having an oxetane group include (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, (3- And butyl-3-oxetanyl) methyl (meth) acrylate, (3-hexyltyl-3-oxetanyl) methyl (meth) acrylate, and the like.
Examples of commercially available products include ETERNACOLL OXMA (manufactured by Ube Industries), OXE-10, OXE-30 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

[Other ethylenically unsaturated monomers]
Other ethylenically unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl, in addition to the ethylenically unsaturated monomer (c1) described above. (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) Alkyl (meth) acrylates such as acrylate and isobornyl (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
N-substituted type (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
And nitriles such as (meth) acrylonitrile. Here, (meth) acrylate refers to methacrylate or acrylate, and (meth) acrylamide refers to methacrylamide or acrylamide.

Monomers that can be used in combination with the above acrylic monomers include styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and acetic acid. And fatty acid vinyls such as vinyl and vinyl propionate.

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

[Synthesis Method (1)]
In the presence of the hydroxyl group-containing compound (a),
A hydroxyl group in a vinyl polymer having two hydroxyl groups in one terminal region obtained by radical polymerization of the ethylenically unsaturated monomer (c);
Dispersant (X) is obtained by reacting an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2).

[Synthesis method (2)]
Generated by reacting a hydroxyl group in the hydroxyl group-containing compound (a) with an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic anhydride (b1) and tricarboxylic anhydride (b2) In the presence of
The dispersant (X) is obtained by radical polymerization of the ethylenically unsaturated monomer (c).

[Synthesis of polyester part X1 ']
The synthesis of the polyester portion X1 ′ is carried out in the acid anhydride group and the hydroxyl group-containing compound (a) in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2). This is a step of reacting the hydroxyl group.

(Reaction catalyst)
As the catalyst used for the production of the polyester portion X1 ′, a known catalyst can be used. As a catalyst, for example,
Triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, or 1,5-diazabicyclo- [4.3.0] Examples thereof include tertiary amine compounds such as -5-nonene, mono-n-butyltin (IV) oxide, and the like.

(Reaction solvent)
For the production of the polyester portion X1 ′, it is possible to produce the polyester portion X1 ′ alone, but it is preferable to use a solvent in order to avoid problems such as high viscosity and non-uniform reaction. There is no limitation in particular as a solvent used, A well-known thing 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. After completion of the reaction, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

(Reaction temperature)
The reaction temperature for the synthesis of the polyester part X1 ′ is 50 ° C. to 180 ° C., preferably 80 ° C. to 140 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and when 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. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but the reaction may be stopped when 97% or more of the acid anhydride is half-esterified by acid value measurement.

[Synthesis of vinyl polymer portion X2 ']
The vinyl polymer portion X2 ′ in the dispersant (X) is obtained by radical polymerization of the ethylenically unsaturated monomer (c). Since this vinyl polymer portion X2 'functions as an affinity site for the solvent and colorant carrier as the side chain of the dispersant (X), it is stable even when fine pigments or dyes are used. It can be made excellent in properties.

The weight average molecular weight of the vinyl polymer portion X2 'is preferably 1000 to 20000, more preferably 2000 to 15000, still more preferably 2000 to 12000, and particularly preferably 3000 to 8000. This portion X2 'becomes an affinity portion for the solvent as the dispersion medium. If the weight average molecular weight of the vinyl polymer portion X2 'is less than 1000, the effect of steric repulsion by the solvent affinity portion is reduced, and it is difficult to prevent pigment aggregation and dispersion stability may be insufficient. On the other hand, if it exceeds 20000, the absolute amount of the solvent affinity part increases, and the dispersibility effect itself may be lowered. Further, the viscosity of the dispersion may increase.

In addition, the content of the ethylenically unsaturated monomer (c) is preferably 3 to 100 parts by weight with respect to 1 part by weight of the hydroxyl group-containing compound (a), and bulk polymerization or solution polymerization is preferably performed. The amount is more preferably 8 to 25 parts by weight, still more preferably 10 to 20 parts by weight. If it exceeds 100 parts by weight, the molecular weight of the vinyl polymer site X2 ′ is too high, and the absolute amount increases as an affinity site for the pigment carrier and the solvent, and the dispersibility effect itself may decrease, When the weight is less than 10 weight, the molecular weight of the vinyl polymer portion X2 ′ is too low, and the effect of steric repulsion is lost as an affinity portion for the pigment carrier and the solvent, and it is difficult to suppress the aggregation of the pigment. There is.

In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer. As the polymerization initiator, an azo compound and an organic peroxide can be used. 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] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxynedecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like. These polymerization initiators can be used alone or in combination of two or more.

In the case of solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, etc. can be used as the polymerization solvent, but it is not particularly limited thereto. It is not something. These polymerization solvents may be used as a mixture of two or more.

As the dispersant (X), known techniques described in International Publication No. 2008/007776, JP-A 2009-155406, JP-A 2011-157416 and the like can be used.

《Other dispersants》
Specific examples of other dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Water-soluble dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester, modified polymer Acrylate, ethylene oxide / propylene oxide addition compounds, phosphate esters, various surfactants, and the like can be used, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto. is not.

The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and acts to stabilize the dispersion of the pigment on the dye carrier by adsorbing to the pigment. It is something to do.
Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nihon Lubrizol, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF EFKA-46, 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., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; Examples thereof include amphoteric surfactants such as alkylbetaines such as aminoacetic acid betaine and alkylimidazolines.

Other dispersants 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)>
The photosensitive coloring composition according to the embodiment of the present invention can contain an adhesion improving agent such as a silane coupling agent in order to improve the adhesion to the transparent substrate. By improving the adhesion with the silane coupling agent, the reproducibility of fine lines is improved and the resolution is improved.
Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and other epoxy silanes, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-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, with respect to 100 parts by weight of the colorant (D) in the photosensitive coloring composition.

<Multifunctional thiol (F)>
The photosensitive coloring composition by embodiment of this invention can contain polyfunctional thiol (F). The polyfunctional thiol (F) is a compound having two or more thiol (SH) groups.
When the polyfunctional thiol (F) is used together with the above-described photopolymerization initiator (A), in the radical polymerization process after light irradiation, a thiyl radical is generated that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen. The resulting photosensitive coloring composition has high sensitivity. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.
For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tris Thioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol Hexhexakis (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 and the like. 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, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the colorant (D).
By using 0.05 part by weight or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Antioxidant>
The photosensitive coloring composition according to the embodiment of the present invention may contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and high coating film transmittance can be obtained.

The “antioxidant” in the embodiment of the present invention may be a compound having an ultraviolet absorption function, a radical scavenging function, or a peroxide decomposition function, and specifically, a hindered phenol type as an antioxidant. Hindered amine, phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylate, and triazine compounds, and known ultraviolet absorbers and antioxidants can be used.

Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.
These antioxidants can be used singly or in combination of two or more at any ratio as required.

The content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition (100% by weight) because the brightness and sensitivity are good.

<Ultraviolet absorber (G), polymerization inhibitor (H)>
The photosensitive coloring composition according to the embodiment of the present invention may contain an ultraviolet absorber (G) or a polymerization inhibitor (H). By containing the ultraviolet absorber (G) or the polymerization inhibitor (H), the shape and resolution of the pattern can be controlled. Examples of the ultraviolet absorber 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, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4- Benzophenone series such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, p-tert-butylphenyl salicylate, Cyanoacrylates such as ethyl-2-cyano-3,3′-diphenylacrylate, 2,2,6,6-tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2,2 , 6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] [ Hindered amines such as (2,2,6,6-tetramethyl-4-piperidinyl) imino] and the like. Properly it is used as a mixture. Examples of the polymerization inhibitor include methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, t-butylcatechol and the like. Hydroquinone derivatives and phenolic compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. Copper and manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxyl Min such nitroso compounds and their ammonium salts or aluminum salts and the like, and used alone or in combination.

The ultraviolet absorber (G) and the polymerization inhibitor (H) are 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the colorant (D) in the coloring composition. Can be used in quantities.
By using 0.01 part by weight or more of the ultraviolet absorber (G) or the polymerization inhibitor (H), better resolution can be obtained.

<Solvent>
In the photosensitive coloring composition according to the embodiment of the present invention, the colorant (D) is sufficiently dispersed in a dye carrier such as the resin (B) or the photopolymerizable compound (C), and then on a transparent substrate such as a glass substrate. In order to make it easy to form a filter segment or a black matrix by applying the film to a dry film thickness of 0.2 to 10 μm, a solvent can be contained. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butylal N-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Recall monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl Tons, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic esters, and the like, used these alone or in mixtures.
The solvent can be used in an amount of 100 to 10,000 parts by weight, preferably 500 to 5000 parts by weight, with respect 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 a storage stabilizer. By containing a storage stabilizer, the viscosity with time of the composition can be stabilized. Examples of the storage stabilizer include 2,6-bis (1,1-dimethylethyl) -4-methylphenol, pentaerystyryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, hindered phenols, tetraethylphosphine, tri Organic phosphines such as phenylphosphine and tetraphenylphosphine, phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate and molybdenum dibutyldithiophosphate, sulfurs such as dodecyl sulfide and benzothiophene, benzyltrimethyl chloride, Quaternary ammonium chloride such as diethylhydroxyamine , Lactic acid, and organic acids and their methyl ethers such as oxalic acid. May be used singly or as a mixture.

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 with respect to 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 temporal stability of the photosensitive coloring composition is improved.

Moreover, the photosensitive coloring composition by embodiment of this invention can be made to contain the amine-type compound which has a function which reduces the dissolved oxygen.
Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

<Production method of photosensitive coloring composition>
The photosensitive coloring composition according to the embodiment of the present invention includes a three-roll mill, a two-roll mill, a sand mill, and a kneader in a pigment carrier such as the resin (B) and / or a solvent, optionally with a colorant (D). In the case of producing a pigment dispersion by finely dispersing using various dispersing means such as an attritor, the photopolymerization initiator (A), the resin (B), the photopolymerizable compound (C), Depending on other photopolymerization initiator (Y), sensitizer (E), polyfunctional thiol (F), UV absorber (G), polymerization inhibitor (H), storage stabilizer, solvent, and other ingredients It can be produced by stirring. Further, the photosensitive coloring composition containing two or more kinds of pigments is prepared by mixing each pigment dispersion separately finely in a dye carrier and / or a solvent, and further mixing a photopolymerization initiator (A) or light. The polymerizable compound (C) and the like can be produced by mixing and stirring.

When dispersing the colorant (D) in the resin (B) and / or solvent, a pigment derivative can be appropriately contained together with an optional dispersant. The pigment derivative is excellent in dispersion of the pigment and has a large effect of preventing reaggregation of the pigment after dispersion. Therefore, the pigment derivative is used together with an optional dispersant to disperse the pigment in the resin (B) and / or the solvent. When the photosensitive coloring composition is used, a color filter excellent in transparency can be obtained.

The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic pigment also includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called pigments. Examples of pigment derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination 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 with respect to 100 parts by weight of the colorant (D).

The photosensitive coloring composition according to the embodiment of the present invention can be prepared in the form of a solvent development type or alkali development type colored resist material. The colored resist material is a composition containing an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (A) and a solvent together with an optional dispersant. It is dispersed.

The photosensitive coloring composition is obtained by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

<Color filter>
Next, the color filter of the present invention will be described.
A color filter according to an embodiment of the present invention includes a filter segment or a black matrix formed from the photosensitive coloring composition of the present invention on a transparent substrate, and a general color filter includes at least one red filter. A segment, at least one green filter segment, and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

As the transparent substrate, a glass plate such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate can be used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.
The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

The formation of each color filter segment and the black matrix by the photolithography method can be performed by the following method. That is, the photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material has a dry film thickness of 0. 0 on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. Apply to 2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer, or spraying the developer with a spray or the like to remove an uncured portion to form a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. After forming, UV exposure can also be performed.

The present invention includes at least the following embodiments.
[1]
Photosensitivity 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). Coloring composition.
General formula (1)

[In General Formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted Alternatively, it represents an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. ]
[2]
The photosensitive coloring composition according to [1], further comprising another photopolymerization initiator (Y).
[3]
The photosensitive coloring according to [2], wherein the other photopolymerization initiator (Y) includes at least one compound selected from the group consisting of an acetophenone compound, a phosphine compound, and an imidazole compound. Composition.
[4]
The photosensitive coloring composition as described in 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], further comprising a polyfunctional thiol (F).
[6]
A color filter comprising a filter segment or a black matrix formed from the photosensitive coloring composition according to any one of [1] to [5] on a transparent substrate.

[7]
It contains a photopolymerization initiator (A) represented by the following general formula (1), a resin (B), a photopolymerizable compound (C), a colorant (D), and a dispersant. A photosensitive coloring composition, wherein at least one selected from the group consisting of a resin (B), a colorant (D), and a dispersant has an oxetane group.
General formula (1)

[In General Formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted Alternatively, it represents an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. ]
[8]
The dispersant has an oxetane group,
The dispersant is
An acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2) is reacted with a hydroxyl group in the hydroxyl group-containing compound (a). Polyester part X1 ′ having a carboxyl group;
It contains a dispersant (X) having a vinyl polymer portion X2 ′ obtained by radical polymerization of an ethylenically unsaturated monomer (c), and the portion X2 ′ has an oxetane group [7 ] The photosensitive coloring composition of description.
[9]
Furthermore, other photoinitiator (Y) is contained, The photosensitive coloring composition as described in [7] or [8] characterized by the above-mentioned.
[10]
The other photopolymerization initiator (Y) contains at least one compound selected from the group consisting of an acetophenone compound, a phosphine compound, and an imidazole compound, and the photosensitive coloring according to [9] Composition.
[11]
The photosensitive coloring composition according to any one of [7] to [10], further comprising a polyfunctional thiol (F).
[12]
A color filter comprising a filter segment or a black matrix formed from the photosensitive coloring composition according to any one of [7] to [11] on a transparent substrate.

Hereinafter, embodiments of the present invention will be specifically described by way of 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 this Example section, and the group of Examples 31 to 52 is described in the latter half. For each group, first, the acrylic resin solutions used in Examples and Comparative Examples and the method for producing the pigment dispersion are described, and then the preparation and evaluation of the photosensitive coloring composition are described. The molecular weight of the resin is the weight average in terms of polystyrene measured using HLC-8220GPC (manufactured by Tosoh Corporation) as the apparatus, TSK-GEL SUPER HZM-N connected in series as the column, and THF as the solvent. Molecular weight. In the examples and comparative examples, “parts” means “parts by weight”.

About Examples 1-30

<Production method of refined green pigment>
(Green refined pigment (G-2))
In a three-necked flask, add 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (7), 500 parts of N-methylpyrrolidone, and 13.9 parts of diphenyl phosphate, and heat to 90 ° C. The reaction was allowed for 8 hours. After cooling this 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 refined pigment (G-3))
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (7), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out 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 collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water, and dried to obtain a pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 10.1 bromine atoms substituted on the resulting phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted 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)

<Method for producing fine blue pigment>
(Blue refined pigment (B-2))
To 1000 parts of 98% sulfuric acid, 90 parts of a crude copper phthalocyanine synthesized by a known method and 10 parts of a dispersant represented by the chemical formula (8) were added and stirred at 30 ° C. for 2 hours. An aqueous solution in which copper phthalocyanine particles were precipitated was obtained by mixing with water. The obtained aqueous solution was stirred for 30 minutes and then filtered, washed with water, dried and pulverized to obtain 95 parts of a blue pigment composition (B-2). The obtained blue pigment composition 1 was confirmed to have an X-ray diffraction pattern of 2θ = 5 to 35 ° with an X-ray diffractometer (RINTKU manufactured by RIGAKU), and found to be around 6.94 ° and 9.76 °. A characteristic peak was confirmed for α-type copper phthalocyanine, and no characteristic peak was confirmed for β-type copper phthalocyanine at around 6.9 °, around 9.0 °, and around 12.4 °. (CIPigment Blue 15) was confirmed.

Formula (8)

(Blue refined pigment (B-3))
85 parts of crude copper phthalocyanine synthesized by a known method, 15 parts of a dispersant represented by the chemical formula (8), 1000 parts of sodium chloride, and 280 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader manufactured by Inoue Seisakusho and kneaded at 70 ° C. for 8 hours. did. After kneading, it was taken out to 20000 parts of a 45 ° C. acetic acid-sodium acetate buffer aqueous solution (pH 4.0), stirred while keeping it warm for 1 hour, filtered, washed with water, dried and ground to obtain 96 parts of a blue pigment composition (B-3). . With respect to the obtained blue pigment composition 2, when an X-ray diffraction pattern of 2θ = 5 to 35 ° was confirmed with an X-ray diffractometer (RINTKU manufactured by Rigaku), about 6.9 °, about 9.0 °, A characteristic peak is confirmed in β-type copper phthalocyanine near 12.4 °, and no characteristic peak is confirmed in α-type copper phthalocyanine near 6.94 ° and 9.76 °. Since no peak characteristic of ε-type copper phthalocyanine near ° and 9.1 ° was confirmed, it was confirmed to be β-type copper phthalocyanine (CIPigment Blue 15: 2).

<Method for Producing Salt-Forming Compound V>
In the following procedure, C.I. I. A salt-forming compound (V) composed of Acid Red 52 and tristearyl monomethylammonium chloride which is a quaternary ammonium salt compound was prepared. C. so as to obtain a 10% aqueous solution. I. Acid Red 52 is dissolved in water and heated to 30 to 50 ° C., then tristearyl monomethylammonium chloride is dissolved in a methanol / water = 20/80 solution to form a 5% solution and added dropwise little by little. Tristearyl monomethylammonium chloride may be used as a solid. After dropwise addition of tristearyl monomethylammonium chloride, the mixture is stirred at 30 to 50 ° C. for 3 hours and sufficiently reacted. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of acid red 52 and tristearyl monomethylammonium chloride, a salt-forming compound (V) was obtained.

<Method for producing acrylic resin solution>
[Preparation of acrylic resin solution]
(Step 1: Polymerization of resin main chain)
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 14 parts styrene, 29 parts dicyclopentanyl methacrylate, 57 parts glycidyl methacrylate, and 1.0 part azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage. The polymerization reaction was carried out dropwise over 2.5 hours.

(Step 2: Reaction to epoxy group)
Next, the inside of the flask was purged with air, and 29 parts of acrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the mixture was heated at 120 ° C. for 5 hours. Reaction was performed and the resin solution whose weight average molecular weight (Mw) is about 10500 was obtained. Since the added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, no carboxyl group is generated in the resin structure.

(Step 3: Reaction to hydroxyl group)
Furthermore, as a catalyst required for the reaction of 46 parts of tetrahydrophthalic anhydride and the precursor at this stage, 0.5 part of triethylamine was added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.

(Step 4: Adjustment of nonvolatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20% by weight to obtain an acrylic resin solution. The weight average molecular weight (Mw) was 11500, and the acid value was 103 mgKOH / g.

<Method for producing pigment dispersion>
[Preparation of red pigment dispersion]
After the mixture having the following composition is uniformly stirred and mixed, it is dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red pigment dispersion PR was prepared.
Diketopyrrolopyrrole pigment (CIPigment Red 254): 7.02 parts ("Irga Four Red B-CF" manufactured by BASF)
Anthraquinone pigment (CI Pigment Red 177): 1.38 parts ("chromofal red A2B" manufactured by BASF)
Nickel azo complex pigment (CI Pigment Yellow 150): 0.80 part ("E4GN" manufactured by LANXESS)
Resin-type pigment dispersant: 2.05 parts (“Solsperse 20000” manufactured by Nippon Lubrizol)
Diketopyrrolopyrrole pigment derivative: 2.00 parts Formula (9)

Acrylic resin solution: 13.75 parts cyclohexanone: 73.00 parts

[Preparation of Green Pigment Dispersion P-G1]
Using a mixture having the following composition, a green pigment dispersion P-G1 was produced in the same manner as the red pigment dispersion.
Zinc phthalocyanine pigment (CIPigment Green 58): 8.95 parts (“FASTOGENGREENA110” manufactured by DIC)
Monoazo pigment (CIPigment Yellow 150)): 2.75 parts ("E4GN" manufactured by LANXESS)
Resin-type pigment dispersant: 4.90 parts (“EFKA4300” manufactured by BASF)
Propylene glycol monomethyl ether acetate: 83.40 parts

[Preparation of green pigment dispersion P-G2]
Using a mixture having the following composition, a green pigment dispersion P-G2 was prepared in the same manner as the red pigment dispersion.
Phthalocyanine pigment G-2: 3.4 parts quinophthalone pigment (CIPigment Yellow 138): 7.6 parts ("Pariotol Yellow K0961HD" manufactured by BASF)
Resin-type pigment dispersant ("BYK-LPN6919" manufactured by Big 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]
Using a mixture having the following composition, a green pigment dispersion P-G3 was produced in the same manner as the red pigment dispersion.
Phthalocyanine pigment G-3: 3.4 parts quinophthalone pigment (CIPigment Yellow 138): 7.6 parts ("Pariotol Yellow K0961HD" manufactured by BASF)
Resin type pigment dispersant ("BYK-LPN6919" manufactured by Big 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 having the following composition, a blue pigment dispersion P-B1 was produced in the same manner as the red pigment dispersion.
ε-type copper phthalocyanine pigment (CIPigment Blue 15: 6): 11.20 parts (“Heliogen Blue L-6700F” manufactured by BASF)
Resin type pigment dispersant: 4.62 parts (“Solsperse 20000” manufactured by Nippon Lubrizol)
Acrylic resin solution: 1.00 parts Cyclohexanone: 83.18 parts

[Preparation of blue pigment dispersion P-B2]
Using a mixture having the following composition, a 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 Nippon Lubrizol)
Acrylic resin solution: 1.00 parts Cyclohexanone: 83.18 parts

[Preparation of blue pigment dispersion P-B3]
Using a mixture having the following composition, a 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 Nippon Lubrizol)
Acrylic resin solution: 1.00 parts Cyclohexanone: 83.18 parts

[Method for producing salt-forming compound-containing resin solution]
(Preparation of salt-forming compound-containing resin solution (SV))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a salt-forming compound-containing resin solution (SV).
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]
A black pigment dispersion P-BK was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.
Carbon black (“MA77” manufactured by Mitsubishi Chemical Corporation): 11.20 parts Resin-type pigment dispersant 3.82 parts (“Solsperse 20000” manufactured by Nippon Lubrizol) Acrylic resin solution: 4.90 parts Cyclohexanone: 80.08 parts

(Preparation of photosensitive coloring composition)
Each material was mixed and stirred at a formulation ratio shown in Tables 1 to 3, and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color.

The symbols in Tables 1 to 3 are shown below.
Photopolymerization initiator A1: Compound having the structure of the following formula (2) Formula (2)

Photopolymerization initiator A2: Compound having the structure of the following formula (3) 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 ("Lucirin TPO" manufactured by BASF)
Photopolymerization initiator Y4: 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (“Biimidazole” manufactured by Kurokin Kasei)
Photopolymerization initiator Y5: ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime)
(BASF "Irgacure OXE02")
・ Sensitizer E1: 2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Sensitizer E2: 4,4′-bis (diethylamino) benzophenone (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.)

Photopolymerizable compound C: dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei 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 Co., Ltd.)
Silane coupling agent S3: 3-acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.)
Multifunctional thiol F1: Trimethylolpropane tri (3-mercaptobutyrate) (“TPMB” manufactured by Showa Denko KK)
Multifunctional thiol F2: pentaerythritol tetrakis (3-mercaptopropionate) (“PEMP” manufactured by Sakai Chemical Industry Co., Ltd.)

Antioxidant G1: 2 pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
("IRGANOX1010" manufactured by BASF)
-Polymerization inhibitor H1: Methyl hydroquinone ("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 4-6.

[Filter segment and black matrix pattern formation]
The obtained photosensitive coloring composition was applied to a 10 cm × 10 cm glass substrate by spin coating, and then the solvent was removed by heating at 70 ° C. for 15 minutes in a clean oven to obtain a coating film of about 2 μm. . Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 30 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive coloring composition, and this was set as an appropriate development time.
The film thickness of the coating film was determined using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[Sensitivity evaluation]
The film thickness of the pattern in the filter segment formed by the above method or the 100 μm photomask portion of the black matrix was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was evaluated. The smaller the minimum exposure, the higher the sensitivity and the better the photosensitive coloring composition.
The rank of evaluation is as follows.
◎: less than ^{30mJ / cm 2 ○: 30mJ /} cm 2 or more 50mJ / cm less than ² △: 50mJ / cm ² or more 100mJ / cm ² less than ×: 100mJ / cm ² or more

[Evaluation of linearity]
The pattern in the 100 μm photomask portion of the filter segment or black matrix formed by the above method was evaluated by observation using an optical microscope. The rank of evaluation is as follows.
○: Good linearity Δ: Partially poor linearity ×: Poor linearity

[Pattern shape evaluation]
The cross section of the pattern in the filter segment or the 100 μm photomask portion of the black matrix formed by the above method was evaluated by observing with an electron microscope. The pattern cross section has good forward taper. The rank of evaluation is as follows.
◎: Forward tapered shape with gentle cross section ○: Cross section with forward tapered shape ×: Cross section with reverse tapered shape

[Resolution evaluation]
The pattern in the 25 μm photomask portion of the filter segment or black matrix formed by the above method was evaluated by observing with an optical microscope. The rank of evaluation is as follows. The poor resolution means that adjacent stripe patterns are connected or chipped. The rank of evaluation is as follows.
◎: Good resolution and linearity ○: Slightly inferior in linearity but good resolution △: Poor linearity and partial chipping ×: Poor resolution

[Development resistance evaluation]
During spray development, measure the pattern film thickness at the 100μm photomask part of the filter segment or black matrix developed by developing twice the appropriate time, and compare with the pattern film thickness formed by developing at the appropriate development time did. The rank of evaluation is as follows. A: Film thickness difference within 20% B: Film thickness difference greater than 20%, within 40%
X: The film thickness difference is larger than 40%. Or chipping or peeling occurs

[Evaluation of chemical resistance]
The filter segment or black matrix formed by the above method is immersed in an N-methylpyrrolidone solution for 30 minutes, then washed with ion-exchanged water, air-dried, and the pattern on the 100 μm photomask portion is observed and evaluated using an optical microscope. went. The rank of evaluation is as follows.
◎: Good with no change in appearance and color ○: Some wrinkles are generated, but good without change in color ×: Peeling or color fading occurs

As shown in Tables 4 to 6, the filter segments and the black matrix formed using the photosensitive coloring compositions of Examples 1 to 30 have good sensitivity, linearity and resolution, and the photopolymerization of the present application. Examples 7 to 10, 12, 16 to 18, 21 to 23, and 27 to 29 used in combination with the initiator (A) and the other photopolymerization initiator (Y) showed superior characteristics depending on the pattern shape. Among them, the other photopolymerization initiator (Y) is 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone. Examples 8, 12, 17, 22, and 23 were further excellent in sensitivity.

Further, Examples 13 to 18, 22, 25, and 26 containing a silane coupling agent (S) were very excellent in adhesion and showed high resolution.

Further, Examples 19 to 21 and 23 containing polyfunctional thiol (F) were excellent in sensitivity.
Further, Examples 3, 5, 25, and 26 further containing an antioxidant (G) or a polymerization inhibitor (H) were excellent in resolution.
When other oxime ester photopolymerization initiators were used as in Comparative Examples 1 and 2, the pattern shape was poor even when the sensitivity was good, and none of the evaluation items were good. .
Moreover, when there was no photopolymerizable compound (C) like the comparative example 3, the poor formation of a filter segment or a black matrix generate | occur | produced, and the thing which became favorable was not obtained.

About Examples 31-52

<Method for producing acrylic resin solution>
[Preparation of acrylic resin solution 1]
(Step 1: Polymerization of resin main chain)
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 14 parts styrene, 29 parts dicyclopentanyl methacrylate, 57 parts glycidyl methacrylate, and 1.0 part azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage. The polymerization reaction was carried out dropwise over 2.5 hours.

(Step 2: Reaction to epoxy group)
Next, the inside of the flask was purged with air, and 29 parts of acrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the mixture was heated at 120 ° C. for 5 hours. Reaction was performed and the resin solution whose weight average molecular weight (Mw) is about 10500 was obtained. Since the added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, no carboxyl group is generated in the resin structure.

(Step 3: Reaction to hydroxyl group)
Furthermore, as a catalyst required for the reaction of 46 parts of tetrahydrophthalic anhydride and the precursor at this stage, 0.5 part of triethylamine was added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.

(Step 4: Adjustment of nonvolatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 20% by weight to obtain an acrylic resin solution. The weight average molecular weight (Mw) was 11500, and the acid value was 103 mgKOH / g.

[Preparation of acrylic resin solution 2])
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of (3-ethyl-3-oxetanyl) methyl methacrylate, 2,2′- A mixture of 1.1 parts of azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Was added to prepare an acrylic resin solution 2. The weight average molecular weight (Mw) was 24000.

<Method for producing resin having cationic group in side chain>
(Resin 1 having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 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, 2,2′-azobis (2,4-dimethylvaleronitrile) ) And 25.1 parts of methyl ethyl ketone were made uniform, charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a cationic group in the side chain having 47% by weight of an ammonium group as the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

(Resin 2 having a cationic group in the side chain)
Resin 2 having a cationic group in the same procedure as the production of resin 1 having a cationic group, except that the raw material was changed to the composition shown in Table 7 in the production of resin 1 having a cationic group in the side chain. Got.

<Dye production method>
(Dye 1)
In the following procedure, C.I. I. Dye 1 which is a salt-forming compound composed of Acid Red 289 and Resin 1 having a cationic group in the side chain was produced.
The resin 1 having a cationic group in a side chain of 30 parts in terms of solid content was added to 2000 parts of water, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 was dissolved was prepared and added dropwise little by little to the resin solution. After dropping, the mixture was stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. Dye 1 which is a salt-forming compound of Acid Red 289 and Resin 1 having a cationic group in the side chain was obtained. At this time, C.I. I. The content of the effective pigment component derived from Acid Red 289 was 27% by weight.

(Dye 2)
In the production of the dye 1, the same procedure as in the production of the dye 1 was followed 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. I. Dye 2 which is a salt-forming compound of Acid Red 289 and Resin 2 having a cationic group in the side chain was obtained.

<Method for producing dispersant>
(Synthesis of dispersant (X-1))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of (3-ethyl-3-oxetanyl) methyl methacrylate, and 45.4 parts of PGMAc. Replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol was added, 0.12 part of AIBN (azobisisobutyronitrile) was further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by solid content measurement. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 part of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added at 120 ° C. For 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. PGMAc was added to adjust the non-volatile content to 50% to obtain a dispersant (X-1) having an acid value of 43 and a weight average molecular weight of 9000.

<Method for producing pigment dispersion>
[Preparation of red pigment dispersion P-R1]
After the mixture having the following composition is uniformly stirred and mixed, it is dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red pigment dispersion PR was prepared.
7.02 parts of diketopyrrolopyrrole pigment (CIPigment Red 254) ("Irga Four Red B-CF" manufactured by BASF)
Anthraquinone pigment (CI Pigment Red 177) 1.38 parts (BASF “chromoftal red A2B”)
Nickel azo complex pigment (CI Pigment Yellow 150) 0.80 parts ("E4GN" manufactured by LANXESS)
Dispersant (X-1) 7.47 parts diketopyrrolopyrrole pigment derivative 2.00 parts

Acrylic resin solution 1 5.33 parts Propylene glycol monomethyl ether acetate 76.00 parts

[Preparation of red pigment dispersion P-R2]
After the mixture having the following composition is uniformly stirred and mixed, it is dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red pigment dispersion PR was prepared.
7.02 parts of diketopyrrolopyrrole pigment (CIPigment Red 254) ("Irga Four Red B-CF" manufactured by BASF)
Anthraquinone pigment (CI Pigment Red 177) 1.38 parts (BASF “chromoftal red A2B”)
Nickel azo complex pigment (CI Pigment Yellow 150) 0.80 parts ("E4GN" manufactured by LANXESS)
2.05 parts of resin-type pigment dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol)
Diketopyrrolopyrrole pigment derivative 2.00 parts

Acrylic resin solution 1 13.75 parts Propylene glycol monomethyl ether acetate 73.00 parts

[Preparation of Green Pigment Dispersion P-G1]
Using a mixture having the following composition, a green pigment dispersion P-G1 was produced in the same manner as the red pigment dispersion.
Zinc phthalocyanine pigment (CIPigment Green 58) 8.57 parts ("FASTOGENGREENA110" manufactured by DIC)
Monoazo pigment (CIPigment Yellow 150)) 2.63 parts ("E4GN" manufactured by LANXESS)
Dispersant (X-1) 7.47 parts acrylic resin solution 1 5.33 parts propylene glycol monomethyl ether acetate 76.00 parts

[Preparation of green pigment dispersion P-G2]
Using a mixture having the following composition, a green pigment dispersion P-G2 was prepared in the same manner as the red pigment dispersion.
Aluminum phthalocyanine pigment (CIPigment Green 63) 3.46 parts quinophthalone pigment (CIPigment Yellow 138) 7.74 parts ("Pariotol Yellow K0961HD" manufactured by BASF)
Dispersant (X-1) 7.47 parts Acrylic resin solution 1 5.33 parts Propylene glycol monomethyl ether acetate 76.00 parts

[Preparation of Blue Pigment Dispersion P-B1]
Using a mixture having the following composition, a blue pigment dispersion P-B1 was produced in the same manner as the red pigment dispersion.
ε-type copper phthalocyanine pigment (CIPigment Blue15: 6) 11.20 parts ("Heliogen Blue L-6700F" manufactured by BASF)
Dispersant (X-1) 7.47 parts Acrylic resin solution 1 5.33 parts Propylene glycol monomethyl ether acetate 76.00 parts

[Preparation of Blue Pigment Dispersion P-B2]
Using a mixture having the following composition, a blue pigment dispersion P-B2 was prepared in the same manner as the red pigment dispersion.
ε-type copper phthalocyanine pigment (CIPigment Blue15: 6) 7.20 parts ("Heliogen Blue L-6700F" manufactured by BASF)
Dye (1) 4.00 parts Resin-type pigment dispersant 4.62 parts ("Solsperse 20000" manufactured by Nippon Lubrizol)
Acrylic resin solution 1 1.00 parts Propylene glycol monomethyl ether acetate 83.18 parts

[Preparation of Blue Pigment Dispersion P-B3]
Using a mixture having the following composition, a blue pigment dispersion P-B3 was prepared in the same manner as the red pigment dispersion.
ε-type copper phthalocyanine pigment (CIPigment Blue15: 6) 7.20 parts ("Heliogen Blue L-6700F" manufactured by BASF)
Dye (2) 4.00 parts Resin-type pigment dispersant 4.62 parts ("Solsperse 20000" manufactured by Nippon Lubrizol)
Acrylic resin solution 1 1.00 parts Propylene glycol monomethyl ether acetate 83.18 parts

[Preparation of Black Pigment Dispersion P-BK]
A black pigment dispersion P-BK was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.
Carbon black (“MA77” manufactured by Mitsubishi Chemical Corporation) 11.20 parts Dispersant (X-1) 7.47 parts Acrylic resin solution 1 5.33 parts Propylene glycol monomethyl ether acetate 76.00 parts

(Preparation of photosensitive coloring composition)
Each material was mixed and stirred at a formulation ratio shown in Tables 8 to 11, and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color.

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

About the obtained photosensitive coloring composition, filter segment and black matrix pattern formation, sensitivity evaluation, linearity evaluation, pattern shape evaluation, resolution evaluation, development resistance evaluation, and chemical resistance evaluation are the examples described above. This was carried out in the same manner as 1-30. The heat resistance was evaluated by the following method.

[Heat resistance evaluation]
The chromaticity ([L * (1), a * (1), b * (1)]) of the filter segment or black matrix C light source formed by the above method is measured with a microspectrophotometer (Olympus Optical Co., Ltd. OSP-SP100 "). Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
The rank of evaluation is as follows.
A: ΔEab * is less than 5.0 ○: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

Evaluation results are shown in Tables 12-14.

As shown in Tables 12 to 14, the filter segments and the black matrix formed using the photosensitive coloring compositions of Examples 31 to 52 have good sensitivity, linearity, resolution, and heat resistance. Examples 37 to 40, 42, 45, 46, and 49 used in combination with other photopolymerization initiator (A) and other photopolymerization initiator (Y) showed superior characteristics depending on the pattern shape. Among them, the other photopolymerization initiator (Y) is 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone. Examples 38, 42 and 46 were more sensitive.

In addition, Examples 43 to 46 containing polyfunctional thiol (F) were excellent in sensitivity.
Further, Examples 33, 35, 47, and 48 further containing an antioxidant (G) or a polymerization inhibitor (H) were excellent in resolution.
When other oxime ester photopolymerization initiators were used as in Comparative Examples 4 and 5, the pattern shape was poor even when the sensitivity was good, and none of the evaluation items were good. .
Moreover, when there was no photopolymerizable compound (C) like the comparative example 6, the filter segment or the black matrix formation defect generate | occur | produced and the thing which became favorable was not obtained.
Further, as in Comparative Examples 7 and 8, when none of the colorant, resin and dispersant contained an oxetane group, the heat resistance was poor.

Claims (8)

1. Photosensitivity 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). Coloring composition.
   General formula (1)
   

   

   [In General Formula (1), R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted Alternatively, it represents an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. ]
2. 2. The photosensitive coloring composition according to claim 1, further comprising a dispersant, wherein at least one selected from the group consisting of the resin (B), the colorant (D) and the dispersant has an oxetane group. object.
3. The dispersant has an oxetane group,
   The dispersant is
   An acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2) is reacted with a hydroxyl group in the hydroxyl group-containing compound (a). Polyester part X1 ′ having a carboxyl group;
   Vinyl polymer portion X2 ′ formed by radical polymerization of ethylenically unsaturated monomer (c)
   A dispersant (X) having
   And the part X2 'has an oxetane group, The photosensitive coloring composition of Claim 2 characterized by the above-mentioned.
4. The photosensitive coloring composition according to any one of claims 1 to 3, further comprising another photopolymerization initiator (Y).
5. The photosensitive coloring according to claim 4, wherein the other photopolymerization initiator (Y) contains at least one compound selected from the group consisting of acetophenone compounds, phosphine compounds, and imidazole compounds. Composition.
6. 6. The photosensitive coloring composition according to claim 1, further comprising a silane coupling agent (S).
7. The photosensitive coloring composition according to any one of claims 1 to 6, further comprising a polyfunctional thiol (F).
8. A color filter comprising a filter segment or a black matrix formed from the photosensitive coloring composition according to any one of claims 1 to 7 on a transparent substrate.