JP2012177826A - Photosensitive colored composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored composition capable of achieving high development durability and high resolution even when a pigment content is high or a film thickness is large, and to provide a color filter using the composition.SOLUTION: With the photosensitive colored composition of the present invention, as a specified compound is used as a photopolymerization initiator in the composition, each color filter segment and a black matrix pattern having high sensitivity and superior properties can be formed even when a pigment content is high or even when the thickness of films of the color filter segment and the black matrix is large. Therefore, a high-quality color filter can be obtained by using the photosensitive colored composition.

Description

  The present invention relates to a photosensitive coloring composition, for example, a photosensitive coloring composition particularly useful for forming red, green and blue filter segments and a black matrix of a color filter used in a liquid crystal display device or a solid-state imaging device. . Moreover, this invention relates to the color filter formed using this photosensitive coloring composition.

The color filter is formed by arranging two or more kinds of fine band-like filter segments having different hues on a transparent substrate such as a glass substrate so as to be parallel to each other (in a stripe shape) or cross each other, or Two or more kinds of fine filter segments having different values are arranged so as to be sequentially arranged in each of the vertical direction and the horizontal direction. The filter segments have small dimensions of several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
Generally, in the manufacture of a color liquid crystal display device, a transparent electrode for driving liquid crystal molecules is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning liquid crystal molecules in a certain direction is further formed thereon. Forming. In order to sufficiently bring out the performance of the transparent electrode and the alignment film, the formation thereof is generally performed 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 not only light resistance but also excellent heat resistance as a colorant is mainly used.
In the pigment dispersion method, a color filter is manufactured by the following method. First, a photosensitive coloring composition (pigment resist) obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. After removing the solvent from the coating by drying, the coating is exposed with a pattern corresponding to a filter segment of a certain color. Subsequently, the unexposed part of this coating film is removed by development, and then a treatment such as heating is performed as necessary. Thereby, a filter segment pattern of the first color is obtained. Then, by performing the same operation as this, filter segment patterns of other colors are formed, and the color filter is completed.

  In recent years, color liquid crystal display devices have been installed in car navigation systems, laptop computers, desktop computer monitors, color television receivers, etc., thanks to their energy-saving and space-saving features, forming a large market. Has led to. A color liquid crystal display device has attracted attention as an alternative to a conventional color cathode ray tube (CRT) display device, but at present, the color reproducibility of a color liquid crystal display device is inferior to that of a color CRT display device. Therefore, the color filter is required to achieve higher color reproducibility.

  In a color filter, a black matrix is generally arranged between filter segments having different hues in order to improve contrast. As this black matrix, a metal chrome black matrix has been conventionally used. However, in recent years, from the viewpoint of environmental problems, low reflectivity, and low cost, resin-made pigments are dispersed in a resin. Black matrix is drawing attention. 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, when the content of the pigment is increased, problems such as a reduction in sensitivity, deterioration in developability and resolution occur. On the other hand, when the film thickness is increased, the exposure light does not reach the bottom of the film, causing problems such as a defective pattern shape.
In order to solve such problems, as described in Patent Documents 1 and 2, generally in photosensitive coloring compositions, (1) provision of a reactive double bond of a resin, (2) photopolymerization Initiators, sensitizers are increased, (3) monomers are selected or increased, and the like.

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 present invention is a photosensitive coloring having high sensitivity, high residual film ratio, high linearity, pattern shape, resolution, development resistance, and chemical resistance even when the pigment content is high or the film thickness is large. An object is to provide a composition and a color filter using the composition.

  The photosensitive coloring composition of the present invention is highly sensitive by using a specific compound as a photopolymerization initiator, and excellent linearity, pattern shape, resolution, development resistance, and chemical resistance can be obtained. The photopolymerization initiator represented by the following general formula (1) 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 contains a resin (B), a photopolymerizable compound (C), a pigment ( D) and a photosensitive coloring composition.
General formula (1)

〔一般式（１）において、Ｘ₁、Ｘ₃〜Ｘ₅は、水素原子、炭素数１〜１２の直鎖状もしくは分岐状のアルキル基、炭素数３〜２０の環状のアルキル基、またはフェニル基を示し、各アルキル基およびフェニル基は、ハロゲン原子、炭素数１〜６のアルコキシル基、およびフェニル基からなる群から選ばれる置換基で置換されていてもよい。Ｘ₂はシクロアルキル基で置換された炭素数１〜２０のアルキル基を表す。〕

[In General Formula (1), X ₁ and X _{3 to} X ₅ are each a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or phenyl Each alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, and a phenyl group. X ₂ represents a C 1-20 alkyl group substituted with a cycloalkyl 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) contains at least one compound selected from the group consisting of an acetophenone compound, a phosphine compound, and an imidazole compound. It relates to a property 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.

Since the photosensitive coloring composition of the present invention uses a specific oxime ester photopolymerization initiator, even if the pigment content is high or the formation thickness of each color filter segment and black matrix is large, the development resistance / Each color filter segment and black matrix pattern excellent in image quality and linearity 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 contains a resin (B), a photopolymerizable compound (C), and a pigment (D). contains.
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.
Furthermore, better chemical resistance 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)

〔一般式（１）において、Ｘ₁、Ｘ₃〜Ｘ₅は、水素原子、炭素数１〜１２の直鎖状もしくは分岐状のアルキル基、炭素数３〜２０の環状のアルキル基、またはフェニル基を示し、各アルキル基およびフェニル基は、ハロゲン原子、炭素数１〜６のアルコキシル基、およびフェニル基からなる群から選ばれる置換基で置換されていてもよい。Ｘ₂はシクロアルキル基で置換された炭素数１〜２０のアルキル基を表す。〕

[In General Formula (1), X ₁ and X _{3 to} X ₅ are each a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or phenyl Each alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, and a phenyl group. X ₂ represents a C 1-20 alkyl group substituted with a cycloalkyl group. ]

  The oxime ester photopolymerization initiator absorbs ultraviolet rays to cleave the N—O bond of the oxime, thereby generating an iminyl radical, a benzoyloxy radical, and an alkyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount.

In the general formula (1), examples of the linear or branched alkyl group having 1 to 12 carbon atoms of X ₁ and X _{3 to} X ₅ include a methyl group, an ethyl group, an n-propyl group, and i-propyl. Group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl Group, n-undecyl group, n-dodecyl group and the like, and examples of the cyclic alkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, Examples thereof include a cycloalkyl group such as a cyclooctadecyl group.

Moreover, as a substituent with respect to each alkyl group and each phenyl group of X < ₁ > and X < ₃ > -X < ₅ >, as an alkoxyl group, for example, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy Group, t-butoxy group and the like, and examples of the halogen atom include a fluorine atom and a chlorine atom.

  Each alkyl group and each phenyl group may be substituted with two or more substituents.

In the general formula (1), X ₁ is preferably a methyl group, an ethyl group, a phenyl group or the like from the viewpoint of the characteristics as a synthetic surface or a colored composition, and X ₃ , X ₄ and X ₅ are each a hydrogen atom. , A methyl group, an ethyl group, an n-propyl group, an i-propyl group, and the like are preferable from the viewpoint of synthesis and characteristics as a colored composition.

X ₂ is an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group, and in particular, an alkyl group substituted with a cyclopentyl group is advantageous in terms of synthesis and stability of the photopolymerization initiator. is there.

As the most preferable structure of the photopolymerization initiator (A), a compound represented by the following formula (2) may be mentioned.
Formula (2)

  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 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 1 to 200 parts by weight, preferably 1 to 150 parts by weight, with respect to 100 parts by weight of the pigment (D) in the photosensitive coloring composition. Can be used in quantities. When the photopolymerization initiator (A) is less than 1 with respect to 100 parts by weight of the pigment (D) in the photosensitive coloring composition, the sensitivity of the photosensitive resin composition is insufficient, and when it is more than 200 parts by weight, This is not preferable because the strength of the film becomes weak.

<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), other photopolymerization initiators (Y) may be used in combination to further improve the chemical resistance. 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 in terms of chemical resistance to contain at least one photopolymerization initiator (Y) selected from the group consisting of acetophenone compounds, phosphine compounds, and imidazole compounds. Among these, the acetophenone compound 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone is further improved in development characteristics. Is also preferable because it is excellent.

  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 200 parts by weight, preferably 1 to 150 parts by weight, based on 100 parts by weight of the pigment (D) in the photosensitive coloring composition.

  Moreover, it can use in the quantity of 1-1000 weight part with respect to 100 weight part of photoinitiators (A). In order to obtain better chemical resistance, an amount of 5 to 600 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. Content of a sensitizer (E) can be used in the quantity of 1-100 weight part with respect to 100 weight part of photoinitiators (A) in a 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.

  Resin (B) can be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of pigment (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 10 to 300 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pigment (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 0.03-1. 00 is preferable, and 0.04 to 0.95 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 0.04 to 1.50, 0 More preferably, it is 0.05 to 1.45.

When [I _a / M] is 0.03 or more and [I _b / M] is 0.04 or more, the sensitivity is high and good. Moreover, when [I _a / M] is 1.00 or less and [I _b / M] is 1.50 or less, the linearity and resolution of the pattern shape are more excellent.

<Pigment (D)>
As the pigment (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.

  Examples of the red photosensitive coloring composition for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, Red pigments such as 255, 264, 272, and 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red photosensitive coloring composition.

Examples of yellow pigments that can be used in combination with the red photosensitive coloring composition include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 1 Or the like can be used 5,176,177,179,180,181,182,185,187,188,193,194,199,213,214.
Moreover, these yellow pigments can be used for the yellow photosensitive coloring composition for forming a yellow filter segment individually or in combination of 2 or more types.

Examples of orange pigments that can be used in combination with the red photosensitive coloring composition include C.I. I. Orange pigments such as Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73 can be used.
Moreover, these orange pigments can be used for the orange photosensitive coloring composition for forming an orange filter segment individually or in combination of 2 or more types.

  Examples of the green photosensitive coloring composition for forming the green filter segment include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37 and 58 can be used. The above-mentioned yellow pigment can be used in combination with the green photosensitive coloring composition.

  Examples of the blue photosensitive coloring composition for forming the blue filter segment include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and 80 can be used. The blue photosensitive coloring composition includes C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

  Examples of the cyan photosensitive coloring composition for forming the cyan filter segment include C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 80 can be used.

  Examples of the magenta color photosensitive coloring composition for forming the magenta color filter segment include C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 81, 144, 146, 177, and 169, and red pigments can be used. A yellow pigment can be used in combination with the magenta photosensitive coloring composition.

  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.

  The photosensitive coloring composition of the present invention may contain a dye within a range that does not reduce heat resistance for color matching.

  Based on the total nonvolatile components of the photosensitive coloring composition of the present invention (100% by weight), the preferable concentration of the pigment (D) component is 10% by weight or more, more preferably from the viewpoint of obtaining sufficient color reproducibility. 15% by weight or more, and most preferably 20% by weight or more. Further, since the stability of the photosensitive coloring composition is improved, the preferable concentration of the pigment (D) component is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less. is there.

<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 pigment (D).
By using 0.05 part by weight or more of polyfunctional thiol, better development resistance can be obtained. If it exceeds 100 parts by weight, the sensitivity may be too high and the resolution may be lowered.

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

<Storage stabilizer (J)>
The photosensitive coloring composition of the present invention can contain a storage stabilizer (J). By containing a storage stabilizer (J), 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 (J) 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 pigment (D) in the coloring composition.
By using 0.01 parts by weight or more of the storage stabilizer (J), the temporal stability of the photosensitive coloring composition is improved.

<Solvent>
In the photosensitive coloring composition of the present invention, the pigment (D) is sufficiently dispersed in a dye carrier such as the resin (B) or the photopolymerizable compound (C), and a dry film thickness is formed on a transparent substrate such as a glass substrate. In order to make it easy to form a filter segment and a black matrix by coating so as to be 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 pigment (D) in the photosensitive coloring composition.

<Other ingredients>
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 pigment (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>
The photosensitive coloring composition of the present invention can be prepared in the form of a solvent developing type or alkali developing type colored resist material. The colored resist material is obtained by finely dispersing the pigment (D) in a dye carrier such as the resin (B) and / or a solvent using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. A pigment dispersion, and the pigment dispersion is subjected to photopolymerization initiator (A), resin (B), photopolymerizable compound (C), and in some cases, other photopolymerization initiator (Y), sensitizer. (E), a polyfunctional thiol (F), an ultraviolet absorber (G), a polymerization inhibitor (H), a storage stabilizer (J), 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 pigment (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 dispersion 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 pigment (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. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include 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 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.

アクリル樹脂溶液 ５．８３部
シクロヘキサノン ８１．６０部 <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) 6.82 parts ("Irga Four Red B-CF" manufactured by Ciba Japan)
1.08 parts of anthraquinone pigment (CI Pigment Red 177) (Chromotal Red A2B manufactured by Ciba Japan)
Nickel azo complex pigment (CI Pigment Yellow 150) 0.88 parts ("E4GN" manufactured by LANXESS)
1.74 parts of resin-type pigment dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol)
Diketopyrrolopyrrole pigment derivative 2.05 parts

Acrylic resin solution 5.83 parts Cyclohexanone 81.60 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.
Halogenated copper phthalocyanine pigment (CI Pigment Green 36) 8.93 parts ("Rionol Green 6YK" manufactured by Toyo Ink 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 5.53 parts Cyclohexanone 80.00 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) 12.88 parts (“Heliogen Blue L-6700F” manufactured by BASF)
5.62 parts of resin-type pigment dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol)
Acrylic resin solution 1.50 parts Cyclohexanone 80.00 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) 11.67 parts resin-type pigment dispersant 2.80 parts (“Solsperse 20000” manufactured by Nippon Lubrizol)
Acrylic resin solution 5.53 parts Cyclohexanone 80.00 parts

[Examples 1-24 and Comparative Examples 1-2]
(Preparation of photosensitive coloring composition)
Each material was mixed and stirred at the prescription ratios shown in Tables 1 to 4, and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color.

光重合開始剤Ｙ１：２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン
（チバ・ジャパン社製「イルガキュア９０７」）
光重合開始剤Ｙ２：２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノン
（チバ・ジャパン社製「イルガキュア３７９」）
光重合開始剤Ｙ３：２，４，６−トリメチルベンゾイル−ジフェニル−ホスフィンオキサイド
（ＢＡＳＦ社製「ルシリンＴＰＯ」）
光重合開始剤Ｙ４：２，２’−ビス（ｏ−クロロフェニル）−４，５，４’，５’−テトラフェニル−１，２’−ビイミダゾール
（黒金化成社製「ビイミダゾール」）
光重合開始剤Ｙ５：ｐ−ジメチルアミノアセトフェノン
（ダイキファイン社製「ＤＭＡ」）
光重合開始剤Ｙ６：１，２−オクタンジオン，１−［４−（フェニルチオ）−，２−（ベンゾイルオキシム）］
（チバ・ジャパン社製「イルガキュアＯＸＥ０１」）
光重合開始剤Ｙ７：ジメチル（２−（４−ジメチルアミノフェニル）２−オキソエチル）スルホニウムブチルトリフェニルボレート
（東洋インキ製造社製「ＴＲＧ−２７８」） Abbreviations in Tables 1 to 4 are shown below.
Photopolymerization initiator A1: Compound formula (2) having the structure of the following formula (2)

Photopolymerization initiator Y1: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“Irgacure 907” manufactured by Ciba Japan)
Photopolymerization initiator Y2: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (“Irgacure 379” manufactured by Ciba Japan) ")
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: p-dimethylaminoacetophenone ("DMA" manufactured by Daiki Fine)
Photopolymerization initiator Y6: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (benzoyloxime)]
("Irgacure OXE01" manufactured by Ciba Japan)
Photopolymerization initiator Y7: dimethyl (2- (4-dimethylaminophenyl) 2-oxoethyl) sulfonium butyltriphenylborate (“TRG-278” manufactured by Toyo Ink Co., Ltd.)

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: trimethylolethane tris (3-mercaptobutyrate)
("TEMB" manufactured by Showa Denko KK)
Multifunctional thiol F2: trimethylolpropane tri (3-mercaptobutyrate)
("TPMB" manufactured by Showa Denko KK)
Multifunctional thiol F3: 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 Ciba Japan)
Ultraviolet absorber G2: 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (“TINUVIN900” manufactured by Ciba Japan)
Polymerization inhibitor H1: N-nitrosophenylhydroxylamine aluminum salt (“Q-1301” manufactured by Wako Pure Chemical Industries, Ltd.)
Polymerization inhibitor H2: Methylhydroquinone (“MH” manufactured by Seiko Chemical Co., Ltd.)

Storage stabilizer J1: 2,6-bis (1,1-dimethylethyl) -4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
Storage stabilizer J2: Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Co., Ltd.)
Organic solvent: cyclohexanone

The obtained photosensitive coloring composition was evaluated by the following methods. The results are shown in Tables 5 and 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 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 50 mJ / cm ² Δ: 50 mJ / cm ² or more and less than 100 mJ / cm ² ×: 100 mJ / 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.
○: Cross section is forward taper shape ×: Cross section is reverse taper 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 △: Partially poor resolution ×: 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.
◎: Film thickness difference within 20% ◯: Film thickness difference greater than 20%, within 40% △: Film thickness difference greater than 40% ×: Chipping or peeling occurs in double development

[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.
◎: Appearance and color are good without change ○: Some wrinkles are generated, but color is good without change Δ: Slight color loss is generated ×: Peeling or color loss is generated

[Stability evaluation over time]
About the obtained photosensitive coloring composition, the viscosity of the initial stage and 1 month after room temperature was measured, and the viscosity increase degree with respect to an initial stage viscosity was calculated and evaluated. The rank of evaluation is as follows.
◎: Viscosity increase rate is 5% or less and good ○: Viscosity increase rate is greater than 5% and less than 10% ×: Viscosity increase rate is greater than 10%

  As shown in Tables 5 and 6, the filter segment and the black matrix formed using the photosensitive coloring compositions of Examples 1 to 25 all had good sensitivity, linearity, and resolution.

  Furthermore, Examples 2-7, 11-17 used in combination with any one of an acetophenone compound, a phosphine compound, or an imidazole compound as the photopolymerization initiator (A) and the other photopolymerization initiator (Y). , 19, 20, 22, 23, 25 exhibited excellent characteristics due to chemical resistance. Among them, the other photopolymerization initiator (Y) is 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (light Examples 3, 4, 11, 13, 15, 16, 20, and 23, which are polymerization initiators Y2), were further excellent in development resistance.

Further, Examples 5, 15, 24, and 25 containing polyfunctional thiol (F) were more excellent in development resistance.
Furthermore, Examples 7, 8, 14, and 20 that further contained the ultraviolet absorber (G) or the polymerization inhibitor (H) were more excellent in resolution.
Further, Examples 16 and 21 containing a storage stabilizer (J) were excellent in stability over time.
When other oxime ester photopolymerization initiators are used as in Comparative Examples 1 and 2, or when there is no photopolymerizable compound (C), defects in pattern characteristics occur, and all are good. It was not obtained.

Claims (5)

Photosensitive coloring characterized by containing a photopolymerization initiator (A) represented by the following general formula (1), a resin (B), a photopolymerizable compound (C), and a pigment (D). Composition.
General formula (1)

[In General Formula (1), X ₁ and X _{3 to} X ₅ are each a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or phenyl Each alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, and a phenyl group. X ₂ represents a C 1-20 alkyl group substituted with a cycloalkyl group. ]   Furthermore, other photoinitiators (Y) are contained, The photosensitive coloring composition of Claim 1 characterized by the above-mentioned.   The photosensitivity according to claim 2, wherein the other photopolymerization initiator (Y) contains at least one compound selected from the group consisting of acetophenone compounds, phosphine compounds, and imidazole compounds. Coloring 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.