JP2017151342A - Photosensitive colored composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored composition having high sensitivity and excellent properties of linearity, pattern profile, resolution, development durability and chemical resistance even when the composition has a high pigment content or a large film thickness, and a color filter using the composition.SOLUTION: The photosensitive colored composition of the present invention allows formation of each color filter segment and a black matrix pattern having high sensitivity, regardless of a high pigment content or a large thickness of a film formed as the color filter segment or the black matrix, by using a specific compound as a photopolymerization initiator. Thereby, a color filter with high quality can be obtained by using the photosensitive colored composition of the present invention.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive coloring composition, and in particular, a color filter used in a liquid crystal display device or a solid-state imaging device, and is a highly sensitive photosensitive material useful for forming each color filter segment such as red, green, and blue, and a black matrix. The present invention relates to a coloring composition. 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 hundreds of 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.
Accordingly, the present invention provides a photosensitive coloring composition having high sensitivity and excellent linearity, pattern shape, resolution, development resistance, and chemical resistance, even if the pigment content is high or the film thickness is large, and The purpose is to provide a color filter using the.

The photosensitive coloring composition of the present invention is expressed by the following general formula (1) in order to obtain high sensitivity and excellent linearity, pattern shape, resolution, development resistance, and chemical resistance. A photopolymerization initiator is used.
That is, the photosensitive coloring composition of the present invention contains a photopolymerization initiator (A) represented by the following general formula (1), and includes a resin (B), a photopolymerizable compound (C), and a colorant. It is a photosensitive coloring composition containing (D).

General formula (1)


[In the general formula (1), R ₁ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group. Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted An arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms. A group, or a substituted or unsubstituted aryl group; ]

  The present invention also relates to the photosensitive coloring composition, further comprising another photopolymerization initiator (Y).

  In the present invention, 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 a coloring composition.

  Moreover, this invention relates to the said photosensitive coloring composition characterized by including polyfunctional thiol (F) further.

  The present invention also 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 of the present invention has a high sensitivity by using a specific oxime ester compound as a photopolymerization initiator, even if the pigment content is high or the formation thickness of each color filter segment and black matrix is large. In addition, each color filter segment and black matrix pattern having excellent linearity, pattern shape, resolution, development resistance, and chemical resistance can be formed.
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 of the present invention contains a photopolymerization initiator (A) represented by the general formula (1), and includes a resin (B), a photopolymerizable compound (C), and a colorant (D). Containing.
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.

<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 is a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted Or an unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted Represents an acyl group or a substituted or unsubstituted amino group.

  Of these, an alkyl group is preferable from the viewpoint of synthesis and characteristics as a coloring composition.

In general formula (1), R ₂ and R ₃ each independently represent a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number. 3 to 20 cyclic alkyl groups, or substituted or unsubstituted aryl groups.

  Among these, an alkyl group substituted with an alkyl group having 3 to 10 carbon atoms or a cycloalkyl group is preferable from the viewpoint of synthesis and characteristics as a coloring composition.

The hydrogen atom of the substituent in R _{1 to} R ₃ 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, cyclohexyla Alkyl groups such as alkyl groups, dimethylamino groups, diethylamino groups, morpholino groups, piperidino groups and other dialkylamino groups, phenylamino groups, p-tolylamino groups and other arylamino groups, methyl groups, ethyl groups, tert-butyl groups In addition to alkyl groups such as dodecyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, and other heterocyclic groups such as furyl groups and thienyl groups, hydroxy groups 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, Trimethylammonium, dimethylsulfonium, trif Cycloalkenyl 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) can 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 believed to decompose the oxime ester moiety by absorbing ultraviolet rays to produce iminyl radicals and alkyloxy radicals, and the radicals of the active species produced 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 the following three reasons, but details are not clear.

  The first reason is that since the photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1), it is composed of two oxime ester moieties in one molecule and generates radicals. It is thought that ability is high.

  The second reason is that the photopolymerization initiator (A) of the present invention has very good ultraviolet absorption performance due to the structure represented by the general formula (1), so that the energy by the given energy beam is extremely high. 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 third 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 a radical of an active species is represented by 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 ˜30 parts by weight.

<Other photopolymerization initiator (Y)>
In the photosensitive coloring composition of the present invention, in addition to the photopolymerization initiator (A) represented by the general formula (1), another photopolymerization initiator (Y) can be used in combination, so that a more favorable pattern shape can be obtained. It is preferable because it 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 benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3 , 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 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, phosphine compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5 ′ -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) ) -4,4 ′, 5,5′-tetra (p-methylphenyl) biimidazole, and other imidazole compounds, 9,10-phenanthrenequinone Quinone compounds such as camphorquinone and ethylanthraquinone, borate compounds, carbazole compounds, titanocene compounds and the like are 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. .
Moreover, it can use in the quantity of 1-3000 weight part with respect to 100 weight part of photoinitiators (A). In order to obtain a better pattern shape, an amount of 5 to 2000 parts by weight is preferable with respect to 100 parts by weight of the photopolymerization initiator (A).

<Sensitizer (E)>
Furthermore, the sensitizer (E) can be contained in the photosensitive coloring composition of the present invention. 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.
As the sensitizer (E), unsaturated ketones represented by chalcone derivatives and 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 derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives Body, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin 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 is used.
The sensitizer (E) may contain two or more sensitizers in any ratio.

<Resin (B)>
The resin (B) contained in the photosensitive coloring composition of the present invention is a resin having 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. The resin (B) includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these can be used alone or in admixture 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 an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

  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 obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, 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 are also used.

  The resin (B) can be used in an amount of 1 to 400 parts by weight, preferably 1 to 300 parts by weight, with respect to 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 of the present invention is a photopolymerizable monomer or oligomer, such as 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-hexanediol jig Sidyl 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 and methylolated melamine (meth) acrylic ester, epoxy (meth) acrylate, urethane acrylate and other acrylic and methacrylic esters, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol di Vinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylform Bromide, acrylonitrile, and the like. 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, with respect to 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 to 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 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 of this invention is shown with a color index number.
Moreover, as a coloring agent (D), dye can be contained in the range which does not reduce heat resistance.

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 9, 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 are each independently 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 an _-SO 2 ^{NHR 13.} R ^{7 to} R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
However, 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. Moreover, the aluminum phthalocyanine pigment etc. which are described in Unexamined-Japanese-Patent No. 2004-333817, 4893859 etc. can also be used, It is not limited to these in particular.

  Examples of the green pigment 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 or 58. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Green 7, 36 or 58. Moreover, the zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like can also 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, and the like. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Yellow 138, 139, 150, 185, and a quinophthalone compound represented by the following general formula (5).
General formula (5)

[In General Formula (5), X1 to X13 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. It is aryl group, -SO ₃ H group, -COOH group, a metal salt of -SO ₃ H group or a -COOH group, an alkyl ammonium salt of the -SO ₃ H group or a -COOH group, which may have a substituent A good phthalimidomethyl group or a sulfamoyl group which may have a substituent is shown. The adjacent groups of X1 to X4 and / or X10 to X13 together form an aromatic ring that may have a substituent. ]

  Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

  Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a ptyl group, an isoptyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group. Group, stearyl group, linear or branched alkyl group such as 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, pendyl group, 4-methylpentyl group, 4-tert-butylbenzyl group, 4-methoxy Examples thereof include an alkyl group having a substituent such as a pendyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

  Examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isoptyloxy group, a tert-butyloxy group, a neopentyloxy group, 2, In addition to linear or branched alkoxyl groups such as 3-dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro Examples include an alkoxyl group having a substituent such as a propoxy group and a benzyloxy group.

  In addition, examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group, an anthranyl group, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p- Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and other aryl groups having a substituent.

Examples of acidic groups include —SO ₃ H and —COOH, and monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. Etc. In addition, as the alkyl ammonium salt of acidic group, quaternary alkyl such as ammonium salt of long-chain monoalkylamine such as octylamine, laurylamine, stearylamine, palmityltrimethylammonium, dilauryldimethylammonium, distearyldimethylammonium salt, etc. An ammonium salt is mentioned.

The “substituent” in the phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent and the sulfamoyl group (H ₂ NSO ₂ —) which may have a substituent "Includes the above halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, and the like.

  The adjacent groups of X1 to X4 and / or X10 to X13 of the general formula (5) are combined to form an aromatic ring which may have a substituent. The aromatic ring herein includes a hydrocarbon aromatic ring and a heteroaromatic ring. The hydrocarbon aromatic ring includes a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and the heteroaromatic ring includes pyridine. And a ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.

  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 the orange pigment 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 are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

"dye"
The photosensitive coloring composition of the present invention can contain a dye within a range that does not lower the heat resistance.
As dyes, azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, methine dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, thiazines Dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, oxazine dyes, perylene dyes, diketopyrrolopyrrole dyes, quinacridone dyes, ansanthrone dyes, isoindolinone Examples thereof include, but are not limited to, dyes based on dyes, isoindoline dyes, indanthrone dyes, coumarin dyes, quinacridone dyes, pyranthrone dyes, flavanthrone dyes, and perinone dyes.

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.
The content of the colorant (D) is preferably 20% by weight or more, more preferably 30% by weight, particularly preferably 35% by weight or more, in the solid content of 100% by weight of the photosensitive coloring composition for color filters of the present invention. If so, 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.

<Multifunctional thiol (F)>
The photosensitive coloring composition of the present invention can contain a 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.

<Ultraviolet absorber (G), polymerization inhibitor (H)>
The photosensitive coloring composition of the present invention can 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, and t-butylcatechol. Hydroquinone derivatives and phenol 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 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 a dry film is formed 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 coating so as to have a 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.
A solvent can be used in the quantity of 100-10000 weight part with respect to 100 weight part of coloring agents (D) in a photosensitive coloring composition, Preferably it is 500-5000 weight part.

<Other ingredients>

<Storage stabilizer>
The photosensitive coloring composition of the present invention can 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], hindered phenols such as 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, 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. Used alone or in combination.

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.

The photosensitive coloring composition 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.
Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, 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.

Moreover, the photosensitive coloring composition of the present invention can contain an amine compound having a function of reducing 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>
In the photosensitive coloring composition of the present invention, the coloring agent (D) is dispersed in a dye carrier such as the resin (B) and / or a solvent with various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. And finely dispersed to produce a pigment dispersion. In the pigment dispersion, a photopolymerization initiator (A), a resin (B), a photopolymerizable compound (C), and in some cases other photopolymerization initiators ( Y), a sensitizer (E), a polyfunctional thiol (F), an ultraviolet absorber (G), a polymerization inhibitor (H), a storage stabilizer, a solvent, and other components can be mixed and stirred. 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 the colorant (D) is dispersed in the resin (B) and / or the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, the photosensitivity obtained by dispersing the pigment in the resin (B) and / or solvent using the dispersion aid. When the coloring composition is used, a color filter having excellent transparency can be obtained.
The dispersing aid 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 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 adsorbs to the pigment to stabilize the dispersion of the pigment on the dye carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF Manufactured by 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, 101,120,150,1501,1502,1503, 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, lauryl sulfate monoethanolamine, 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; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more.

  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 the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

  The photosensitive coloring composition 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 obtained by dispersing the colorant (D) in a composition containing an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (A), and a solvent. It is.

  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.
The color filter of the present invention comprises 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 has at least one red filter segment, at least It comprises one green filter segment and at least one blue filter segment, or comprises at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are 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.

  Formation of each color filter segment and black matrix by photolithography is 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. It apply | coats so that it may become 2-10 micrometers. 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 by spraying or the like to remove uncured portions and forming 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.

  EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, “parts” means “parts by weight”.

  First, prior to the examples, the acrylic resin solutions used in the examples and comparative examples and the method for producing the pigment dispersion will be described. In addition, the molecular weight of the resin was measured in terms of polystyrene measured using HLC-8220GPC (manufactured by Tosoh Corporation) as a device, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. Weight average molecular weight.

<Method for producing acrylic resin solution>
[Preparation of acrylic resin solution]
370 parts of cyclohexanone was put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate at the same temperature, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A resin solution was obtained.
After cooling to room temperature, about 2 g of acrylic resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized acrylic resin solution so that the nonvolatile content was 20% by weight. Added. The weight average molecular weight of the obtained acrylic resin was 40000.

<Method for producing pigment dispersion>
[Preparation of red pigment dispersion]
After uniformly stirring and mixing the mixture having the following composition, it was dispersed for 5 hours with an Eiger mill (Eiger Japan's “Mini Model M-250 MKII”) 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 (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 13.75 parts Cyclohexanone 73.00 parts

[Preparation of green pigment dispersion]
A green pigment dispersion PG was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.
8.46 parts of halogenated copper phthalocyanine pigment (CI Pigment Green 36) (“Rionol Green 6YK” manufactured by Toyocolor Co., Ltd.)
Monoazo pigment (CI Pigment Yellow 150) 2.74 parts ("E4GN" manufactured by LANXESS)
2.80 parts of resin-type pigment dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol)
Acrylic resin solution 10.00 parts Cyclohexanone 76.00 parts

[Preparation of blue pigment dispersion]
A blue pigment dispersion P-B was prepared in the same manner as the red pigment dispersion using a mixture having the following composition.
ε-type copper phthalocyanine pigment (CIPigment Blue15: 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 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

[Examples 1 to 19 and Comparative Examples 1 to 3]
(Preparation of photosensitive coloring composition)
Each material was mixed and stirred at a prescription ratio shown in Tables 1 to 3, and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color.

[Examples 1 to 19 and Comparative Examples 1 to 3]
(Preparation of photosensitive coloring composition)
Each material was mixed and stirred at a prescription ratio shown in Tables 1 to 3, and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color.

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

Photopolymerization initiator A2: Compound formula (3) having the structure of the following formula (3)

Photopolymerization initiator Y1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“IRGACURE 907” manufactured by BASF)
Photopolymerization initiator Y2: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“IRGACURE 379” manufactured by BASF)
Photopolymerization initiator Y3: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide ("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 (Nippon Kayaku Co., Ltd. “Kayacure DETX-S”)
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.)
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.)

UV absorber G1: 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine ("TINUVIN400" manufactured by BASF)
Polymerization inhibitor H1: Methylhydroquinone (“MH” manufactured by Seiko Chemical Co., Ltd.)

Organic solvent: cyclohexanone

The obtained photosensitive coloring composition was evaluated by the following methods. The results are shown in Tables 4 and 5.
[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 pattern film thickness at the filter segment or the black matrix 100 μm photomask portion formed by the above method was measured, and the minimum exposure amount of 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

[Linearity evaluation]
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 at the 100 μm photomask portion of the filter segment or black matrix formed by the above method was observed and evaluated using 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, the pattern film thickness is measured by developing the pattern film thickness at the filter segment or black matrix 100μm photomask portion formed by developing twice the appropriate time, and developing at the appropriate development time. Compared with. 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 and 5, the filter segment and the black matrix formed using the photosensitive coloring compositions of Examples 1 to 19 have good sensitivity, linearity, and resolution, and the photopolymerization of the present application. Examples 7 to 10, 12, 15, 16, and 18 used in combination with the initiator (A) and the other photopolymerization initiator (Y) showed excellent characteristics due to 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, and 16 were further excellent in sensitivity.

In addition, Examples 13 to 16 including polyfunctional thiol (F) were excellent in sensitivity.
Further, Examples 3 and 5 containing an ultraviolet absorber (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, even if the sensitivity was good, the pattern shape was poor, and everything that was good was not obtained.
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.

Claims (5)

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 the general formula (1), R ₁ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted Or an 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, a substituted or unsubstituted aryl It represents a sulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms. A group, or a substituted or unsubstituted aryl group; ]   Furthermore, other photoinitiators (Y) are contained, The photosensitive coloring composition of Claim 1 characterized by the above-mentioned.   3. The photosensitive coloring according to claim 2, wherein 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. Composition.   Furthermore, polyfunctional thiol (F) is included, The photosensitive coloring composition of any one of Claims 1-3 characterized by the above-mentioned.   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 4 on a transparent substrate.