JP2010256891A - Photosensitive coloring composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition, capable of attaining high developing durability and high definition, even when pigment content is high or the film thickness is large, and to provide a color filter using the same. <P>SOLUTION: The photosensitive coloring composition contains (A) a pigment; (B) a transparent resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator represented by formula (1), wherein X<SP>1</SP>, X<SP>3</SP>and X<SP>6</SP>each independently represent R11, OR11, COR11 or CN, and the like, X<SP>2</SP>represents a 1-20C alkyl group, which may have a substituent, a 7-30C arylalkyl group, which may have a substituent, or a 2-20C heterocyclic group, which may have a substituent, X<SP>4</SP>and X<SP>5</SP>each independently represent R11, OR11, SR11, COR11, CONR12R13, CN, a halogen atom or a hydroxyl group, R11, R12 and R13 each independently represent a hydrogen atom, a 1-20C alkyl group, which may have a substituent, a 7-30C arylalkyl group, which may have a substituent, or a 2-20C heterocyclic group, which may have a substituent, (a) and (b) each independently are an integer from 0 to 3, and as necessary, (E) a sensitizer and (F) a polyfunctional thiol. The color filter is constituted of a filter segment, formed with a photosensitive coloring composition and/or a black matrix on a transparent substrate. <P>COPYRIGHT: (C)2011,JPO&INPIT

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, there is a limit to the improvement of developability and resolution or the improvement of sensitivity only by these methods. In particular, when the amount of the photopolymerization initiator is increased, coloring due to the color of the photopolymerization initiator itself, 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 provides a photosensitive coloring composition capable of achieving high development resistance and high resolution and linearity even when the pigment content is high or the film thickness is large, and a color filter using the same The purpose is to provide.

The photosensitive coloring composition of the present invention is a photopolymerization initiator represented by the following formula (1) in order to be highly sensitive and excellent in internal curing so as to obtain a wrinkle-free shape on the coating film surface. Use.
That is, the photosensitive coloring composition according to one aspect of the present invention includes a pigment (A), a transparent resin (B), a photopolymerizable compound (C), and a photopolymerization start represented by the following formula (1). It contains the photoinitiator (D) containing an agent.

〔式（１）において、Ｘ1、Ｘ3及びＸ6は、それぞれ独立に、Ｒ11、ＯＲ11、ＣＯＲ11、ＳＲ11、ＣＯＮＲ12Ｒ13又はＣＮを表し、Ｘ2は、置換基を有していてもよい炭素原子数が１〜２０のアルキル基、置換基を有していてもよい炭素原子数が６〜３０のアリール基、置換基を有していてもよい炭素原子数が７〜３０のアリールアルキル基又は置換基を有していてもよい炭素原子数が２〜２０の複素環基を表し、Ｘ4及びＸ5は、それぞれ独立に、Ｒ11、ＯＲ11、ＳＲ11、ＣＯＲ11、ＣＯＮＲ12Ｒ13、ＮＲ12ＣＯＲ11、ＯＣＯＲ11、ＣＯＯＲ11、ＳＣＯＲ11、ＣＯＳＲ11、ＣＯＳＲ11、ＣＳＯＲ11、ＣＮ、ハロゲン原子又は水酸基を表す。Ｒ11、Ｒ12及びＲ13は、それぞれ独立に、水素原子、置換基を有していてもよい炭素原子数が１〜２０のアルキル基、置換基を有していてもよい炭素原子数が６〜３０のアリール基、置換基を有していてもよい炭素原子数が７〜３０のアリールアルキル基又は置換基を有していてもよい炭素原子数が２〜２０の複素環基を表す。ａ及びｂは、それぞれ独立に、０〜３の整数である。〕 In addition, a color filter according to another aspect of the present invention includes at least one of a filter segment and a black matrix formed from the photosensitive coloring composition.
Formula (1):

[In Formula (1), X1, X3 and X6 each independently represent R11, OR11, COR11, SR11, CONR12R13 or CN, and X2 represents an optionally substituted carbon atom having 1 to 1 carbon atoms. 20 alkyl groups, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent or a substituent. X4 and X5 each independently represents R11, OR11, SR11, COR11, CONR12R13, NR12COR11, OCOR11, COOR11, SCOR11, COSR11, COSR11, CSOR11, CN, a halogen atom or a hydroxyl group is represented. R11, R12 and R13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 30 carbon atoms which may have a substituent. An arylalkyl group having 7 to 30 carbon atoms which may have a substituent and a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. a and b are each independently an integer of 0 to 3. ]

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 which concerns on one form of this invention is demonstrated.
The photosensitive coloring composition which concerns on one form of this invention is a photopolymerization initiator represented by the pigment (A), transparent resin (B), photopolymerizable compound (C), and said Formula (1). Containing a photopolymerization initiator (D).

<Pigment (A)>
As the pigment (A), organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance is preferable. Usually, an organic pigment is used.
Below, the specific example of the organic pigment which can be used for this photosensitive coloring composition 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 the yellow pigment that can be used in combination with the red pigment in 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 It can be used 5,176,177,179,180,181,182,185,187,188,193,194,199,213 or 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 the orange pigment that can be used in combination with the red pigment in the red photosensitive coloring composition include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61, 71, or 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 or 58 can be used. In addition to this green pigment, the 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 or 80 can be used. In addition to this blue pigment, C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42 or 50 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: 3, 15: 4, 15: 6, 16 or 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 or 19 and other purple pigments and C.I. I. Red pigments such as Pigment Red 81, 144, 146, 177 or 169 can be used. In addition to these purple pigments and red pigments, the 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, or perylene black pigment. I. Pigment Black 1, 6, 7, 12, 20, or 31 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. Carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, you may further use a blue pigment and a purple pigment for a black photosensitive coloring composition.

The carbon black preferably has a specific surface area in the range of 50 to 200 m ² / g by the BET (Brunauer-Emmett-Teller) method from the viewpoint of the shape of the black matrix. If carbon black having a small specific surface area is used, the shape of the black matrix may be deteriorated. On the other hand, when carbon black having a large specific surface area is used, the dispersion aid is excessively adsorbed on the carbon black, so that the blending amount of the dispersion aid necessary for developing various physical properties increases.

In addition, carbon black having a dibutyl phthalate (hereinafter referred to as “DBP”) oil absorption of 120 ml / 100 g or less is preferable and a DBP oil supply of less is preferable from the viewpoint of sensitivity.
The average primary particle diameter of carbon black is preferably in the range of 20 to 50 nm. Carbon black having a small average primary particle size is difficult to disperse at a high concentration, and it is difficult to obtain a black photosensitive coloring composition having good temporal stability. On the other hand, when carbon black having a large average primary particle size is used, the black matrix shape may be deteriorated.

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

The photosensitive coloring composition may contain a dye within a range that does not reduce heat resistance for color matching.
The concentration of the pigment (A) in all the non-volatile components of the photosensitive coloring composition is preferably 10% by weight or more, more preferably 15% by weight or more, and most preferably from the viewpoint of obtaining sufficient color reproducibility. Is 20% by weight or more. In addition, the concentration of the pigment (A) in all the nonvolatile components of the photosensitive coloring composition is preferably 90% by weight or less, more preferably 80% by weight or less, from the viewpoint of the stability of the photosensitive coloring composition. And most preferably not more than 70% by weight.

<Transparent resin (B)>
The transparent resin (B) contained in the photosensitive coloring composition preferably has a transmittance of 80% or more over the entire wavelength region of 400 to 700 nm, particularly over the entire visible light region. More preferably, it is 95% or more. As the transparent resin (B), a thermoplastic resin, a thermosetting resin, or a photosensitive resin 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, and polyimide resins.
Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include a (meth) acryl 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, and an amino group. A resin obtained by reacting a compound or cinnamic acid and introducing a photocrosslinkable group such as a (meth) acryloyl group and a styryl group into the linear polymer is used. Examples of the photosensitive resin include linear polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer, hydroxyalkyl (meth) acrylate and the like. Those half-esterified with a (meth) acrylic compound having a hydroxyl group are also used.

In this specification, when the expression “(meth) acryl” is used for a certain compound, the compound is a compound obtained by replacing “(meth) acryl” with “acryl”, and “(meth) acryl”. "Is replaced with" methacryl ", which means that any of the compounds may be used. Further, in this specification, when the expression “(meth) acrylo” is used for a certain functional group, the functional group is a functional group obtained by replacing “(meth) acrylo” with “acrylo”, and “( It means that any of the functional groups obtained by replacing “meth) acrylo” with “methacrylo” may be used. Further, in this specification, when the expression “(meth) acrylate” is used for a certain compound, the compound is a compound in which “(meth) acrylate” is replaced with “acrylate”, and “(meth) acrylic”. "Is replaced with" methacrylate "which means any compound.
The transparent resin (B) is used in an amount of, for example, 20 to 400 parts by weight, preferably 50 to 250 parts by weight with respect to 100 parts by weight of the pigment (A).

<Photopolymerizable compound (C)>
The photopolymerizable compound (C) is a photopolymerizable monomer or oligomer. Examples of the photopolymerizable compound (C) include methyl (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 diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate Neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate and Various acrylates or methacrylates such as urethane acrylate; (meth) acrylic acid; styrene; vinyl acetate; hydroxyethyl vinyl ether; ethylene glycol divinyl ether; pentaerythritol trivinyl ether; (meth) acrylamide; N-hydroxymethyl (meth) Examples include acrylamide; N-vinylformamide; and acrylonitrile. These can be used alone or in admixture of two or more.
The photopolymerizable compound (C) is used in an amount of, for example, 10 to 300 parts by weight, preferably 10 to 200 parts by weight with respect to 100 parts by weight of the pigment (A).

<Photopolymerization initiator (D)>
(Photopolymerization initiator represented by formula (1))
The photopolymerization initiator (D) is characterized by containing a compound represented by the following formula (1) generally called an oxime ester.
Formula (1):

In the formula (1), X1, X3 and X6 each independently represent R11, OR11, COR11, SR11, CONR12R13 or CN. X2 has an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent. Or an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. Here, the alkyl group having 1 to 20 carbon atoms which may have a substituent and the arylalkyl group having 7 to 30 carbon atoms which may have a substituent are an unsaturated bond. , An ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond and a urethane bond may be present in the methylene chain, or may have a ring structure. X4 and X5 each independently represent R11, OR11, SR11, COR11, CONR12R13, NR12COR11, OCOR11, COOR11, SCOR11, COSR11, COSR11, CSOR11, CN, a halogen atom or a hydroxyl group. R11, R12 and R13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 30 carbon atoms which may have a substituent. An arylalkyl group having 7 to 30 carbon atoms which may have a substituent and a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. Here, the alkyl group having 1 to 20 carbon atoms which may have a substituent and the arylalkyl group having 7 to 30 carbon atoms which may have a substituent are an unsaturated bond, One or more of an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond and a urethane bond may be present in the methylene chain, and it may have a ring structure. a and b are each independently an integer of 0 to 3.

  X1 is particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, from the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability of the photosensitive coloring composition. Alkyl groups having 10 or less carbon atoms such as isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group and 2-ethylhexyl group; carbon such as cyclopentyl group and cyclohexyl group A cyclic alkyl group which may have a side chain having 10 or less atoms; or a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a 2- (1-methoxypropyl) group and a 2- (1-ethoxypropyl) group An alkyl group having 10 or less carbon atoms and having one ether bond in the methylene chain.

X3 is particularly preferably hydrogen from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability of the photosensitive coloring composition; methyl; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl. An alkyl group having 6 or less carbon atoms such as a group, an isobutyl group, a t-butyl group, an n-amyl group, an isoamyl group, a t-amyl group and an n-hexyl group; a carbon atom number such as a cyclopentyl group and a cyclohexyl group. 6 or less cyclic alkyl groups; or methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2- (1-methoxypropyl) group, 2- (1-ethoxypropyl) group and the like have 6 or less carbon atoms And an alkyl group having one ether bond in the methylene chain.

  X2 and X6 are particularly preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n-butyl group from the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability of the photosensitive coloring composition. Alkyl groups having 6 or less carbon atoms such as isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group and n-hexyl group; 6 carbon atoms such as cyclopentyl group and cyclohexyl group. The following cyclic alkyl groups; or the number of carbon atoms such as methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2- (1-methoxypropyl) group and 2- (1-ethoxypropyl) group is 6 or less and An alkyl group having one ether bond in the methylene chain.

X4 and X5 are particularly preferably hydrogen or methyl group, ethyl group, n-propyl group, isopropyl group from the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability of the photosensitive coloring composition. , An n-butyl group, an isobutyl group, a t-butyl group, an n-amyl group, an isoamyl group, a t-amyl group, an n-hexyl group and the like, and an alkyl group having 6 or less carbon atoms.

Preferable specific examples of the photopolymerization initiator represented by the above formula (1) include the following compounds.

Although there is no restriction | limiting in particular in the synthesis method of the photoinitiator represented by the said Formula (1), The following methods can be utilized.
<Step 1>
Synthesis of acyl compounds:
Nitrocarbazole compound 1 and acid chloride 2 are reacted in the presence of aluminum chloride (AlCl 3) to obtain acyl compound 3 which is the target product.
<Step 2>
Synthesis of compound represented by formula (1):
Acyl compound 3, hydroxylamine hydrochloride and dimethylformamide (DMF) are mixed, and this mixture is heated and stirred to obtain oxime compound 4. Next, the oxime compound (oxime ester) 4 and the acid anhydride 5 are heated and stirred to react them. After completion of the reaction, the photopolymerization initiator represented by the above formula (1) is obtained by neutralization with alkali.

By using the photopolymerization initiator represented by the above formula (1), a photosensitive coloring composition having excellent development resistance and color filter production stability can be obtained. By using the photosensitive coloring composition containing this photopolymerization initiator, a high-quality filter segment and black matrix can be formed.
The photopolymerization initiator represented by the above formula (1) absorbs ultraviolet rays to cleave the N—O bond of the oxime to generate iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount. Furthermore, since it has an absorption wavelength in the range of 330 nm to 430 nm due to the nitrocarbazole group, high reaction efficiency is exhibited over a wide wavelength range from the ultraviolet region to the visible region. Further, -C ₆ H ₃ in the formula ^{(1) (X 3) OX} 2 site is believed to enhance the development resistance.
The photopolymerization initiator represented by the formula (1) is used in an amount of, for example, 1 to 100 parts by weight, preferably 2 to 50 parts by weight with respect to 100 parts by weight of the pigment (A).

  By using the photopolymerization initiator represented by the above formula (1), a photosensitive coloring composition having excellent development resistance and capable of improving the production stability of the color filter is obtained. By using the photosensitive coloring composition containing this photopolymerization initiator, a high-quality filter segment and black matrix can be formed.

(Other polymerization initiators)
In said photosensitive coloring composition, in addition to the photoinitiator represented by said Formula (1), another photoinitiator can be used together.
Examples of the additional photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) Acetophenone compounds such as methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin compounds such as ether and benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 3,3 ', Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-meth) Xylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine and 2,4-trichloromethyl (4 Triazine compounds such as' -methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)] And oxime ester compounds such as o- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds;
Or titanocene compounds and the like are used. These additional photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

  Particularly preferred photopolymerization initiators include, for example, α-aminoalkylacetophenone photopolymerization initiators. Examples of the α-aminoalkylacetophenone photopolymerization initiator include 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-butanone , Or a mixture containing two or more thereof can be used. Use of such a photopolymerization initiator is advantageous in obtaining an excellent color filter having no wrinkles on the surface of the coating film.

The additional photopolymerization initiator described above is, for example, 5 to 25 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the photopolymerization initiator represented by the above formula (1). Use.

  As a photoinitiator (D), only 1 type of photoinitiators represented by the said Formula (1) may be used, and 2 or more types may be used. Moreover, when using combining the photoinitiator represented by Formula (1), and another photoinitiator, content of a photoinitiator (D) is 100 weight part of pigments (A). 1 to 200 parts by weight, preferably 2 to 150 parts by weight.

<Sensitizer (E)>
The photosensitive coloring composition can further contain a sensitizer (E). The content of the sensitizer (E) can be used, for example, in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (D).
Examples of the sensitizer (E) include unsaturated ketones typified by chalcone derivatives and dibenzalacetone; 1,2-diketone derivatives typified by benzyl and camphorquinone; benzoin derivatives; fluorene derivatives; Anthraquinone derivative; anthraquinone derivative; xanthene derivative; thioxanthene derivative; xanthone derivative; thioxanthone derivative; coumarin derivative; ketocoumarin derivative; cyanine derivative; merocyanine derivative; Derivatives; indoline derivatives; azulene derivatives; azurenium derivatives; squarylium derivatives; porphyrin derivatives; tetraphenylporphyrin derivatives; Tetrapyrazinoporphyrazine derivative; phthalocyanine derivative; tetraazaporphyrazine derivative; tetraquinoxalyloporphyrazine derivative; naphthalocyanine derivative; subphthalocyanine derivative; pyrylium derivative; thiopyrylium derivative; tetraphyrin derivative; Spirooxazine derivatives; thiospiropyran derivatives; metal arene complexes; organoruthenium complexes; and Michler's ketone derivatives.

Furthermore, specific examples of the sensitizer (E) include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), And sensitizers described in “Special Function Materials” (1986, CMC) edited by Tadasaburo Ikemori et al., But the sensitizer (E) is not limited thereto. The composition may further contain a sensitizer that absorbs light in the ultraviolet to near infrared region.
Among the sensitizers (E), examples of the sensitizer capable of particularly suitably sensitizing the photopolymerization initiator (D) include thioxanthone derivatives and Michler ketone derivatives. More specifically, for example, 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, and 3,6 -Dibenzoyl-N-ethylcarbazole is used.
The sensitizer (E) may contain two or more sensitizers at an arbitrary ratio.

In the photosensitive coloring composition, the ratio Ia / M between the weight Ia of the photopolymerization initiator (D) and the weight M of the photopolymerizable compound (C) is preferably 0.05 to 0.50, and 0 It is more preferably 0.05 to 0.25, and particularly preferably 0.10 to 0.20.
When the photosensitive coloring composition contains the sensitizer (E), the total weight Ib of the photopolymerization initiator (D) and the sensitizer (E) and the weight M of the photopolymerizable compound (C) The ratio Ib / M is preferably 0.10 to 0.60, more preferably 0.10 to 0.37, and particularly preferably 0.12 to 0.30.
When the ratio Ia / M or Ib / M is small, it is difficult to achieve high development resistance. When the ratio Ia / M or Ib / M is large, it is difficult to achieve an excellent pattern shape.

<Multifunctional thiol (F)>
It is preferable that said photosensitive coloring composition further contains polyfunctional thiol (F). The polyfunctional thiol (F) may be a compound having two or more thiol (SH) groups.
When used with the above-mentioned photopolymerization initiator (D), the polyfunctional thiol (F) acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates a thiyl radical that is not easily inhibited by oxygen. Therefore, if the polyfunctional thiol (F) is further contained, the photosensitive coloring composition becomes more sensitive. In particular, polyfunctional aliphatic thiols in which SH groups are bonded to aliphatic groups such as methylene and ethylene groups are preferred. Examples of the polyfunctional aliphatic thiol bonded to the aliphatic group include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycol. Rate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthio Propionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazi And 2- (N, N- dibutylamino) -4,6-dimercapto--s- triazine. Among these, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate and pentaerythritol tetrakisthiopropionate are preferable.
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 determined so that the effect as a chain transfer agent is sufficiently exhibited and the developability and adhesion are not impaired. The content of the polyfunctional thiol (F) is preferably 0.05 to 100 parts by weight and more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the pigment (A). .

<Solvent>
The photosensitive coloring composition may contain a solvent. When a solvent is used, it becomes easy to sufficiently disperse the pigment (A) in the transparent resin (B) and the photopolymerizable compound (C). Further, when a solvent is used, for example, it becomes easy to form a filter segment or a black matrix by applying a dry film thickness of 0.2 to 10 μm on a transparent substrate such as a glass substrate.
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, 2- Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butane Diol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-di Chlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyla Coal, 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, 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 Glycol 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 isobuty Ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid esters. These are used alone or in combination.

<Other ingredients>
The photosensitive coloring composition may further contain a storage stabilizer in order to stabilize the viscosity with time of the composition. The photosensitive coloring composition may further contain an adhesion improving agent such as a silane coupling agent in order to improve the adhesion to the transparent substrate.
Moreover, in order to control the shape of a pattern, said photosensitive coloring composition can contain a ultraviolet absorber and a polymerization inhibitor.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine; organic acids such as lactic acid and oxalic acid; methyl ethers of these organic acids; t-butyl pyrocatechol, tetraethylphosphine and tetraphenylphosphine. Organic phosphines such as fins; and phosphites.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane; (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4- Epoxy cyclohexyl) epoxy silanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane; N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- β (aminoethyl) γ Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane And aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane; and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent is used in an amount of, for example, 0.1 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the pigment (A).

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] [ And hindered amines such as (2,2,6,6-tetramethyl-4-piperidinyl) imino]. Used in or in combination. 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 and the polymerization inhibitor 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 (A) in the coloring composition.

The photosensitive coloring composition may further contain an amine compound that can act to reduce dissolved oxygen.
Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-benzoic acid 2- Examples include dimethylaminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Production method of photosensitive coloring composition>
A photosensitive coloring composition is manufactured with the following method, for example. First, the pigment (A) is finely dispersed in the transparent resin (B) and / or solvent using various dispersing means to prepare a pigment dispersion. Examples of the dispersing means include a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. Next, to this pigment dispersion, a transparent resin (B), a photopolymerizable compound (C) and a photopolymerization initiator (D) are optionally added, and further a sensitizer (E) and a polyfunctional thiol (F). Mix the solvent and other ingredients and stir the mixture. Thereby, a photosensitive coloring composition is obtained. In addition, the photosensitive coloring composition containing two or more kinds of pigments is, for example, mixed with a plurality of pigment dispersions obtained by finely dispersing the pigments separately in the transparent resin (B) and / or solvent. It can be obtained by further mixing the photopolymerization initiator (D), the photopolymerizable compound (C) and the like with the mixture and stirring the mixture.

When the pigment is dispersed in the transparent resin (B) and / or the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant and a pigment derivative can be appropriately contained. The dispersion aid is excellent in the ability to disperse the pigment and has a great effect of preventing reaggregation of the pigment after dispersion. Therefore, when a photosensitive coloring composition in which a pigment is dispersed in the transparent resin (B) and / or a solvent using a dispersion aid is used, a color filter excellent in transparency can be easily obtained.
The dispersing aid is used in an amount of, for example, 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 (A).

  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 pigment carrier, and acts to stabilize the dispersion of the pigment on the pigment carrier by adsorbing to the pigment. It is a resin. Examples of the resin-type pigment dispersant include polyurethane; polycarboxylic acid ester such as polyacrylate; unsaturated polyamide; polycarboxylic acid; polycarboxylic acid (partial) amine salt; polycarboxylic acid ammonium salt; Polysiloxane; long-chain polyaminoamide phosphate; hydroxyl group-containing polycarboxylic acid ester; modified products thereof; amide formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof, etc. (Meth) acrylic acid-styrene copolymer; (meth) acrylic acid- (meth) acrylic ester copolymer; styrene-maleic acid copolymer; water-soluble resin such as polyvinyl alcohol and polyvinylpyrrolidone Or water-soluble polymer compound; Ethers; modified polyacrylates, ethylene oxide / propylene oxide addition compound; or phosphoric ester is used. These can be used alone or in admixture of two or more.

  Examples of commercially available resin-type pigment dispersants include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by Big Chemie. 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000 and 2001, Anti-Terra-U, 203 and 204, BYK-P104, P104S and 220S, Lactimon, Lactimon-WS and Bykumen etc. SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, manufactured by Nippon Lubrizol 2000, 32500, 32600, 34750, 36600, 38500, 41000, 41090 and 53095, etc .; and EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, manufactured by Efka Chemicals 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, and 1503.

  Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate. , Anionic surface activity such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer and polyoxyethylene alkyl ether phosphate Agents: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polio Nonionic surfactants such as ciethylene alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; and Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines. These can be used alone or in admixture of two or more.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. The organic pigment also includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which 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. Can be used. These can be used alone or in admixture of two or more.

From the photosensitive coloring composition, 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 dusts by means of centrifugal separation, sintered filter, membrane filter, etc. Is preferably removed.
The photosensitive coloring composition can be prepared in the form of a solvent developing type or alkali developing type colored resist material. For example, the colored resist material contains a pigment (A) in a composition containing an alkali-soluble transparent resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent. It is dispersed.

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

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

The filter segment and the black matrix are formed by the photolithography method, for example, by the following method.
First, a photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate so that the dry film thickness is, for example, 0.2 to 10 μm. For the application of the colored resist material, a coating method such as spray coating, spin coating, slit coating, or roll coating is used.

  After drying the coating film as necessary, a mask having a predetermined pattern is placed in contact with or away from the coating film, and the coating film is irradiated with light such as ultraviolet rays through the mask. . For example, a mercury lamp is used as the light source. Alternatively, instead of performing exposure using a photomask, laser beam drawing is performed on the coating film. For example, a laser that outputs a laser beam having a wavelength of 300 to 410 nm is used. As the laser, a known laser including a semiconductor laser; a solid-state laser such as a YAG (yttrium-aluminum-garnet) laser; and a gas laser such as an argon laser, a helium neon laser, a carbon dioxide gas laser, and an excimer laser can be used. The exposed portion of the coating film is cured by exposure using this mask or laser beam drawing.

Next, the coating film is immersed in a solvent or an alkaline developer, or the developer is sprayed on the coating film to remove an unexposed portion which is an uncured portion from the coating film. As the alkali developer, for example, an aqueous solution such as sodium carbonate and sodium hydroxide is used, and an organic alkali such as dimethylbenzylamine and triethanolamine can also be used. An antifoaming agent and a surfactant can also be added to the developer. As the development processing method, for example, a shower development method, a spray development method, a dip (immersion) development method, or a paddle (liquid accumulation) development method can be used.
Thereafter, the pattern obtained by development is heated as necessary to accelerate the polymerization reaction. Each of the filter segments and the black matrix is thus obtained.
According to this photolithography method, it is possible to form the filter segment and the black matrix with higher accuracy than the printing method.

  In addition, after the coating film is dried and before the coating film is exposed, a water-soluble or alkali-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, is applied onto the previous coating film and dried. May be. A coating film made of a water-soluble or alkali-soluble resin prevents oxygen from inhibiting the polymerization reaction during exposure. Therefore, when this coating film is formed, the sensitivity of the coating film made of the photosensitive coloring composition to exposure light can be increased.

  Examples of the present invention will be described below. It should be understood that these examples are intended to facilitate understanding and implementation of the present invention and are not intended to limit the scope of the present invention. In the examples and comparative examples, “part” means “part by weight”.

  First, preparation of acrylic resin solutions used in Examples and Comparative Examples will be described. In addition, the molecular weight of the resin described below is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography). Specifically, the molecular weight of the resin described below is HLC-8220GPC (manufactured by Tosoh Corp.) manufactured by Tosoh Corporation, and TSK-GEL SUPER HZM-N is used as a column connected in series with two solvents. Is a weight average molecular weight in terms of polystyrene measured using THF (tetrahydrofuran).

[Preparation of acrylic resin solution]
370 parts of cyclohexanone was poured into the reaction vessel and heated to 80 ° C. while injecting nitrogen gas into the reaction vessel. At this temperature, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate, 15.0 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis are contained in the reaction vessel. A mixture of 4.0 parts of isobutyronitrile was added dropwise over 1 hour to cause a polymerization reaction. After completion of dropping, this was left for 3 hours while maintaining the temperature at 80 ° C. Thereafter, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added to this liquid. This liquid was allowed to stand at a temperature of 80 ° C. for 1 hour to cause a reaction, thereby obtaining an acrylic resin solution.
After the acrylic resin solution was cooled to room temperature, about 2 g thereof was sampled and heated at a temperature of 180 ° C. for 20 minutes to measure the nonvolatile content. Using this measurement result, cyclohexanone was added to the previously synthesized acrylic resin solution so that its nonvolatile content was 20% by weight. The weight average molecular weight of the obtained acrylic resin was 40000.

[Preparation of pigment dispersion]
The pigment, the resin-type pigment dispersant, the pigment derivative, the acrylic resin, and the solvent were uniformly mixed by stirring at the weight ratio shown in the column labeled “PR” in Table 1 below. Subsequently, this mixed solution was subjected to a dispersion treatment for 5 hours by a sand mill using zirconia beads having a diameter of 1 mm. Furthermore, it filtered with the filter and the coarse particle | grains whose diameter is 5 micrometers or more were removed from this dispersion liquid. Thereby, a red pigment dispersion PR was obtained.
Also, the red pigment dispersion PR was used except that the pigment, the resin-type pigment dispersant, the acrylic resin, and the solvent were mixed in the weight ratios shown in the columns “PG”, {PB ”, and“ PBK ”in Table 1 below. A green pigment dispersion PG, a blue pigment dispersion PB, and a black pigment dispersion PBK were respectively prepared by the same method as described above.

アクリル樹脂溶液：
先に調製したアクリル樹脂溶液
有機溶剤：
シクロヘキサノン The substances represented by abbreviations or general names in Table 1 are specifically as follows.
PR254:
Diketopyrrolopyrrole pigment (CIPigment Red 254)
("Irga Four Red B-CF" manufactured by Ciba Japan)
PR177:
Anthraquinone pigment (CIPigment Red 177)
(Chromo Tar Red A2B manufactured by Ciba Japan)
PG36:
Halogenated copper phthalocyanine pigment (CIPigment Green 36)
("Rionol Green 6YK" manufactured by Toyo Ink Co., Ltd.)
PY150:
Nickel azo complex pigment (CIPigment Yellow 150)
("E4GN" manufactured by LANXESS)
PB15: 6:
ε-type copper phthalocyanine pigment (CIPigment Blue 15: 6)
("Heliogen Blue L-6700F" manufactured by BASF)
CB:
Carbon black (CIPigment Black 7)
("MA11" manufactured by Mitsubishi Chemical Corporation)
Resin type pigment dispersant:
“Solsperse 20000” manufactured by Nippon Lubrizol
Pigment derivatives:
Diketopyrrolopyrrole pigment derivative formula (2) represented by the following formula (2):

Acrylic resin solution:
Acrylic resin solution organic solvent prepared earlier:
Cyclohexanone

[Preparation of photosensitive coloring composition]
The materials of the photosensitive coloring composition were mixed according to the formulation (weight ratio) shown in Table 2. After sufficiently stirring, the mixture was filtered through a filter to remove coarse particles having a diameter of 1 μm or more from the dispersion. As described above, photosensitive coloring compositions RR1 to RR25, RG1 to RG9, RB1, RB2, RBK1 and RBK2 were prepared.

Pigment dispersion: previously prepared acrylic resin solution: previously prepared acrylic resin solution polyfunctional thiol: trimethylolpropane tristhiopropionate photopolymerization initiator W: photopolymerization initiator represented by formula (3) Photopolymerization initiator Y: photopolymerization initiator represented by formula (4) Photopolymerization initiator T: photopolymerization initiator represented by formula (5) Photopolymerization initiator V: represented by formula (6) Photopolymerization initiator Photopolymerization initiator Z: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (o-acetyloxime)]
("Irgacure OXE02" manufactured by Ciba Japan)
Photopolymerization initiator P: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1
[4- (4-morpholinyl) phenyl] -1-butanone
("Irgacure 379" manufactured by Ciba Japan)
Photopolymerization initiator Q: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one
("Irgacure 907" manufactured by Ciba Japan)
Photoinitiator R: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
("Lucirin TPO" manufactured by BASF)

Sensitizer F1: 2,4-Diethylthioxanthone
(“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Sensitizer F2: 4,4'-bis (diethylamino) benzophenone
("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
UV absorber H1: 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)
UV absorber H2: 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol
("TINUVIN900" manufactured by Ciba Japan)

Polymerization inhibitor G1: N-nitrosophenylhydroxylamine aluminum salt (“Q-1301” manufactured by Wako Pure Chemical Industries, Ltd.)
Polymerization inhibitor G2: Methylhydroquinone
(“MH” manufactured by Seiko Chemical Co., Ltd.)
Photopolymerizable compounds: dipentaerythritol penta and hexaacrylate
("Aronix M402" manufactured by Toagosei Co., Ltd.)
Solvent: cyclohexanone

[Synthesis of photopolymerization initiators W, Y, T and V]
Said photoinitiator W, Y, T, and V was synthesize | combined with the following method.
Synthesis of photopolymerization initiator W <Step 1> Synthesis of acyl compound In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, and 53 mmol of N-ethyl-3-nitro-carbazole Were put into an ice-cooled reaction vessel. While maintaining the reaction temperature at 5 ° C. or lower, 64 mmol of 4- (2-methoxy-1-methyl-ethoxy) -2-methyl-benzoyl chloride was gradually added dropwise to the mixture. After completion of the dropwise addition, the mixed solution was stirred at 20 ° C. for 4 hours. Thereafter, the reaction liquid was poured into ice water to separate into an oily phase and an aqueous phase, and the liquid constituting the oily phase was dried using magnesium sulfate. Next, the desiccant was removed from the liquid by filtration, and the solvent was removed by distillation. The acyl body was obtained as described above.
<Step 2> Synthesis of photopolymerization initiator W In a nitrogen stream, 20 mmol of the acyl compound, 2.1 g (30 mmol) of hydroxylamine hydrochloride, and 16.9 g of dimethylformamide were charged into a reaction vessel. The mixture was stirred at 80 ° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent constituting the oily phase was removed by distillation, and then 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added to the distillation residue. The mixture was stirred at 90 ° C. for 1 hour, then cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil / water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as the solvent. The photoinitiator W was obtained as mentioned above.

Synthesis of photopolymerization initiator Y <Step 1> Synthesis of acyl compound In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, and N- (2-ethyl-hexyl) -3 -53 mmol of nitrocarbazole compound was put into an ice-cooled reaction vessel. While maintaining the reaction temperature at 5 ° C. or lower, 64 mmol of 4- (2-methoxy-1-methyl-ethoxy) -2-methyl-benzoyl chloride was gradually added dropwise to the mixture. After completion of the dropwise addition, the mixed solution was stirred at 20 ° C. for 4 hours. Thereafter, the reaction liquid was poured into ice water to separate into an oily phase and an aqueous phase, and the liquid constituting the oily phase was dried using magnesium sulfate. The desiccant was removed from this liquid by filtration, and the solvent was removed by distillation. The acyl body was obtained as described above.
<Step 2> Synthesis of Photopolymerization Initiator Y In a nitrogen stream, 20 mmol of the acyl compound, 2.1 g (30 mmol) of hydroxylamine hydrochloride, and 16.9 g of dimethylformamide were charged into a reaction vessel. The mixture was stirred at 80 ° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent constituting the oily phase was removed by distillation, and then 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added to the distillation residue. The mixture was stirred at 90 ° C. for 1 hour, then cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil / water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as the solvent. As described above, a photopolymerization initiator Y was obtained.

Synthesis of photopolymerization initiator T <Step 1> Synthesis of acyl compound In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, and 53 mmol of N-ethyl-3-nitrocarbazole compound Were put into an ice-cooled reaction vessel. While maintaining the reaction temperature at 5 ° C. or lower, 64 mmol of 4- (ethoxymethyl) -2-methyl-benzoyl chloride was gradually added dropwise to the mixture. After completion of the dropwise addition, the mixed solution was stirred at 20 ° C. for 4 hours. Thereafter, the reaction liquid was poured into ice water to separate into an oily phase and an aqueous phase, and the liquid constituting the oily phase was dried using magnesium sulfate. The desiccant was removed from this liquid by filtration, and the solvent was removed by distillation. The acyl body was obtained as described above.
<Step 2> Synthesis of photopolymerization initiator T In a nitrogen stream, 20 mmol of the acyl compound, 2.1 g (30 mmol) of hydroxylamine hydrochloride, and 16.9 g of dimethylformamide were charged into a reaction vessel. The mixture was stirred at 80 ° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent constituting the oily phase was removed by distillation, and then 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added to the distillation residue. The mixture was stirred at 90 ° C. for 1 hour, then cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil / water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as the solvent. As described above, a photopolymerization initiator T was obtained.

Synthesis of photopolymerization initiator V <Step 1> Synthesis of acyl compound In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, and N- (2-ethyl-hexyl) -3 -53 mmol of nitrocarbazole compound was put into an ice-cooled reaction vessel. While maintaining the reaction temperature at 5 ° C. or lower, 64 mmol of 4- (2-methoxy-1-methyl-ethoxy) -2-methyl-benzoyl chloride was gradually added dropwise to the mixture. After completion of the dropwise addition, the mixed solution was stirred at 20 ° C. for 4 hours. Thereafter, the reaction liquid was poured into ice water to separate into an oily phase and an aqueous phase, and the liquid constituting the oily phase was dried using magnesium sulfate. The desiccant was removed from this liquid by filtration, and the solvent was removed by distillation. The acyl body was obtained as described above.
<Step 2> Synthesis of photopolymerization initiator V In a nitrogen stream, 20 mmol of the acyl compound, 2.1 g (30 mmol) of hydroxylamine hydrochloride, and 16.9 g of dimethylformamide were charged into a reaction vessel. The mixture was stirred at 80 ° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent was removed from the liquid constituting the oily phase by distillation, and then 25.4 g of butyl acetate and 3.12 g (24 mmol) of propionic anhydride were added to the distillation residue. The mixture was stirred at 90 ° C. for 1 hour, then cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil / water separation, the solvent was removed from the liquid constituting the oily phase by distillation, and recrystallization was performed using ethyl acetate as the solvent. The photoinitiator V was obtained as mentioned above.

式（４）：

式（５）：

式（６）：

Formula (3):

Formula (4):

Formula (5):

Formula (6):

[Examples 1 to 30 and Comparative Examples 1 to 8]
Each photosensitive coloring composition was evaluated by the following method. The results are shown in Table 3.

(Filter segment and black matrix pattern formation)
Each photosensitive coloring composition was spin-coated on a 10 cm × 10 cm glass substrate, and then the solvent was removed from the photosensitive coloring composition by pre-baking at 70 ° C. for 15 minutes using a clean oven. Thereby, a coating film having a thickness of about 2 μm was obtained. After cooling the substrate to room temperature, the coating film was exposed to ultraviolet rays with an illuminance of 25 mW / cm ² through a photomask. An ultra-high pressure mercury lamp was used as the ultraviolet light source. The photomask used was a layout of a pattern area for evaluating linearity and development resistance and a pattern area for resolution evaluation. Here, the pattern area for evaluating linearity and development resistance is an area in which a plurality of line patterns having a width of 100 μm as light transmission portions are provided in a stripe shape. The resolution evaluation pattern region is a region in which 10 line patterns having a width of 25 μm as light transmission portions are provided in a stripe shape at a pitch of 50 μm. Subsequently, the exposed coating film was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. Then, the post-baking for 30 minutes was performed at 230 degreeC using clean oven. In this way, a filter segment and a black matrix each including a resolution evaluation pattern and a linearity and development resistance evaluation pattern were obtained.
The minimum development time for removing the unexposed area was defined as development time A, and the development time twice as long as development time A was defined as development time B. The minimum exposure amount at which the residual film ratio [= film thickness after post-baking / dried film thickness before development] when developing at development time A was 90% or more was defined as the minimum exposure amount.

(Resolution evaluation)
The stripe pattern for resolution evaluation was observed using an optical microscope, and the resolution was evaluated in the following three stages. Here, poor resolution means that adjacent line patterns are connected or a part of the line pattern is missing.
○: Good resolution △: Partially poor resolution ×: Poor resolution

(Linearity evaluation)
The stripe pattern for evaluating linearity and development resistance was observed using an optical microscope, and the linearity was evaluated in the following three stages.
○: Good linearity △: Partially poor linearity ×: Poor linearity

(Development resistance evaluation)
About development tolerance, the remaining film rate of the stripe pattern for linearity and development tolerance evaluation was computed, and the following four steps evaluated. Here, the residual film ratio is the ratio of the thickness of the coating film after post-baking to the thickness of the dried coating film before development when developing with the development time A or B.
○: Remaining film ratio is 90% or more Δ: Remaining film ratio is 70% or more X: Remaining film ratio is 50% or more and less than 70% XX: Remaining film ratio is less than 50%

(Coating surface wrinkle evaluation)
About the coating surface wrinkle, the stripe pattern for linearity and development tolerance evaluation was observed using the optical microscope, and the state of the coating surface was evaluated in three stages.
○: Coating film surface good △: Coating film surface is slightly rough ×: Wrinkles on coating film surface

As shown in Table 3, the filter segment and the black matrix formed using the photosensitive coloring compositions of Examples 1 to 30 have some differences depending on the formulation, but all have resolution, linearity, and development. There was no practical discoloration in resistance and surface wrinkles. That is, the photosensitive coloring composition using the photopolymerization initiator represented by the general formula (1) (photopolymerization initiators W, Y, T, and V) has excellent development resistance and good pattern linearity. there were. On the other hand, when other oxime ester photopolymerization initiator (photopolymerization initiator Z) is used, the development margin is small, and when the development time is doubled, the development resistance is poor, and the linearity of the pattern and A resolution failure also occurred.
Further, as shown in Examples 1 to 30, particularly excellent development resistance could be achieved by appropriately setting the ratio Ia / M or Ib / M.
Furthermore, as shown in Examples 5 to 7, a photopolymerization initiator represented by the general formula (1) (photopolymerization initiators W, Y, T and V) and an α-aminoalkylacetophenone photopolymerization initiator By using together, it was possible to obtain a good filter segment free from wrinkles on the coating film surface.

Claims (6)

It contains a pigment (A), a transparent resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D) containing a photopolymerization initiator represented by the following formula (1). A photosensitive coloring composition.
Formula (1):

[In Formula (1), X1, X3 and X6 each independently represent R11, OR11, COR11, SR11, CONR12R13 or CN, and X2 represents an optionally substituted carbon atom having 1 to 1 carbon atoms. 20 alkyl groups, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent or a substituent. X4 and X5 each independently represents R11, OR11, SR11, COR11, CONR12R13, NR12COR11, OCOR11, COOR11, SCOR11, COSR11, COSR11, CSOR11, CN, a halogen atom or a hydroxyl group is represented. R11, R12 and R13 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a carbon atom having 6 to 30 carbon atoms which may have a substituent. An arylalkyl group having 7 to 30 carbon atoms which may have a substituent and a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. a and b are each independently an integer of 0 to 3. ]   The ratio Ia / M between the weight Ia of the photopolymerization initiator (D) and the weight M of the photopolymerizable compound (C) is in the range of 0.05 to 0.50. The photosensitive coloring composition as described in 2.   3. The photosensitive coloring composition according to claim 1, wherein the photopolymerization initiator (D) further contains an α-aminoalkylacetophenone photopolymerization initiator.   Further, a sensitizer (E) is contained, and the ratio Ib / M between the total weight Ib of the photopolymerization initiator (D) and the sensitizer (E) and the weight M of the photopolymerizable compound (C) is 0.00. It exists in the range of 10-0.60, The photosensitive coloring composition of any one of Claims 1-3 characterized by the above-mentioned.   Furthermore, polyfunctional thiol (F) is included, The photosensitive coloring composition of any one of Claims 1-4 characterized by the above-mentioned.   A color filter comprising at least one of a filter segment and a black matrix formed from the photosensitive coloring composition according to claim 1.