TW201042378A - Photosensitive colored composition and color filter - Google Patents

Abstract

Provided are a photosensitive colored composition and a color filter using thereof, wherein the photosensitive colored composition has high developing tolerance and high resolution even if the photosensitive colored composition contains high content of pigment or thickness of film is thick. The photosensitive colored composition of the present invention contains pigment, a transparent resin, a photopolymerizing compound and at least one photopolymerizing initiator represented by any one of formula (1) to (3).

Description

201042378 VI. Description of the Invention: [Technical Field] The present invention relates to a photosensitive coloring composition relating to red, green and color forming a color filter such as a liquid crystal display device or a solid-state imaging device. A particularly useful photosensitive coloring composition such as a blue filter segment and a black matrix. Further, the present invention relates to a color filter formed using the photosensitive coloring composition. [Prior Art] The color filter sheet is formed on a transparent substrate such as a glass substrate, and two or more kinds of fine ribbon filter segments having different hue are arranged in parallel (striped) or intersecting each other, or The fine filter segments in which two or more kinds of hue are different are arranged such that they are arranged in the longitudinal direction and the lateral direction in this order. The filter segments are of a size ranging from a few micrometers to hundreds of micrometers, and each color phase is neatly arranged in a predetermined arrangement. Generally, a color liquid crystal display device is fabricated on a color filter by forming a transparent electrode for driving liquid crystal molecules by evaporation or sputtering, and further forming thereon for aligning liquid crystal molecules in a certain direction. Orientation film. In order to sufficiently exhibit the performance of the transparent electrode and the alignment film, it is usually necessary to carry out the formation at a high temperature of 20 ° C or higher, preferably 23 ° C or higher. Therefore, as a method for producing a color filter, a method called a pigment dispersion method is mainly used. The pigment dispersion method uses a pigment which is not only light resistance but also excellent in heat resistance as a colorant. Further, the "pigment dispersion method" was carried out by using the following method to produce a color filter. First, a photosensitive coloring composition (pigment photoresist) which is obtained by dispersing a pigment in a photosensitive transparent resin solution is applied to a transparent substrate such as glass. 201042378 After the solvent is removed from the coating film by drying, the coating film is exposed using a pattern of a calender sheet section corresponding to a certain color. Then, the unexposed portion of the coating film is removed by development, and then, a treatment such as heating is performed as necessary. « This is used to obtain the filter section of the first color. Further, a color filter is obtained by performing the same operation as this to form filter segments of other colors. In recent years, color liquid crystal display devices have been installed in automobile guidance systems, laptop computers, desk top computers, computer monitors, and color television image receivers because of their energy-saving and space-saving features. Form a vast market. The color liquid crystal display device has been attracting attention as a replacement for the conventional color cathode ray tube (CRT) display device, but the color reproduction characteristics of the color liquid crystal display device are currently inferior to those of the color CRT display device. Therefore, color-color liquid crystal display devices are required to achieve higher color reproduction characteristics. • Also, in order to improve contrast, color filters are usually arranged with black matrices between filter sections of different hue. In the black matrix, a black matrix made of a metal chrome has been used in the past, but in recent years, a resin composed of a light-shielding pigment dispersed in a resin dye has been used from the viewpoint of environmental problems, low reflectance, and cost reduction. The black matrix is attracting attention. However, the resin black matrix has a problem that the light blocking property (optical density) is low compared to the black matrix made of metal chrome. In order to improve the color reproduction characteristics of the color filter and to improve the light-shielding 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 pigment content is increased, there is a problem that the sensitivity is lowered, and the development and resolution of the image are deteriorated. On the other hand, increasing the film thickness causes the exposed light to fail to reach the bottom of the film, causing the pattern shape to become a problem of 201042378. In order to solve such a problem, high sensitivity of a photosensitive coloring composition is necessary. Therefore, the development of the photosensitive coloring composition is described in Japanese Unexamined Patent Publication (KOKAI) Publication No. JP-A------ The addition of the resin reactive double bond, (2) the photopolymerization initiator and the sensitizer, or (3) the selection of the most appropriate monomer or monomer increment. SUMMARY OF THE INVENTION However, only the above methods are used to improve the visibility and resolution or the sensitivity of the liter is limited. In particular, when the photopolymerization initiator is increased, the coloring due to the pigment of the photopolymerization initiator itself, the heat resistance are lowered, the light transmittance is lowered, and the resolution is lowered. Further, when the monomer is increased, problems such as adhesion may occur. In view of the above, the present invention provides a photosensitive coloring composition capable of achieving high development resistance and high resolution even when the pigment content is high or the film thickness is large, and a color filter using the same. In order to achieve the above object, the photosensitive coloring Q composition of one aspect of the present invention uses at least one photopolymerization initiator selected from the group consisting of compounds represented by the following formulas (1) to (3) (D). ). In other words, the photosensitive coloring composition of one aspect of the present invention is characterized in that it contains a pigment (A), a transparent resin (B), a photopolymerizable compound (C), and is selected from the following formulas (1) to (3). At least one photopolymerization initiator (D) of the group consisting of the compounds shown. Further, a color filter according to another aspect of the invention is characterized by comprising at least one of a filter segment and a black matrix formed by the photosensitive coloring composition. Equation (1):

[In the formula (Π'χ^χ3 and X6 each independently represents Rn, 〇Rii, COR11, SR11, CONR12R13 or CN, and X2 represents an alkyl group having 1 to 20 carbon atoms which may also have a substituent group, An aryl group having 6 to 30 carbon atoms which may have a substituent, an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, X4 And X5 each independently represent R11, OR11, SR11, C0R11, CONR12R13, NRUCOR11, OCOR11, COOR11, SCOR11, ❹COSR11, COSR11, CSOR11, CN, a halogen atom or a hydroxyl group, and r", R12 and R13 are each independently represented a hydrogen atom, 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 an aromatic group having 7 to 3 carbon atoms which may have a substituent. A mercapto group or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, and 3 and b systems* each independently represent an integer of 〇 to 3] 201042378 Formula (2):

[In the formula (2) and the formula (3), X1 to X4 each independently represent an 'Atom or an alkyl group having 1 to 3 carbon atoms'. Since the photosensitive coloring composition described above contains a photopolymerization initiator in particular, when it is used, high image development resistance and resolution can be formed even when the filter portion or the black matrix of the wafer having a high pigment content is high. The filter segment or the black matrix is thus a color filter that can be used by using the photosensitive coloring composition. [Embodiment] First, the photosensitive coloring of one embodiment of the present invention is described. The photosensitive coloring composition (A), the transparent resin (B), and the photopolymerizable compound (C) of one embodiment of the present invention are selected from (3) At least one kind of light composed of a group of compounds, an atom, a halogen compound, or a color filter has an excellent pattern. A high quality composition is obtained. Contains a pigment. Polymerization initiator of the above formula (1) 201042378 (D). <Pigment (A)> As the pigment (A), an organic or inorganic pigment can be used alone or in a mixture of 2 g or more. Among the pigments, a pigment having high color developability and high heat resistance, and a pigment having high heat decomposition resistance are preferable. Organic pigments are usually used. Hereinafter, a specific example of the organic pigment which can be used for the photosensitive coloring composition is represented by a color index number. In the red photosensitive coloring for forming the red filter segment, the group Q can be used, for example, C. I. Pigment Red 7, 9, 14, 4, 4 8 : 1, 4 8 : 2. 48:3, 48:4, 8 1:1,8 1 :2 ' 8 1 :3,97,122,123,146, 149, 168 '177> 178, 1 79 , 1 80 , 184 , 185 ' 1 87, 192, 200, 202, 208 ' 2 10 '215 > 216 , 217 , 220 ' 223 , 224 , 226 , 227 , 228 , 240 , 242 , 246 , 254 , 2 5 5 , 264 , 272 and 279 etc . Red pigment. Sensitive in red, sexual composition, in addition to the red pigment, the composition can be used in combination with at least one of yellow pigment and orange pigment. As a yellow pigment in the red color, the composition can be used, for example, CI. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16丨' 1 7 ' 1 8 , 20 , 24 , 3 1 , 32 , 34 , 35 , : 3 5:1 , 36 , 36:1 , 37 , 37:1 , 40 , . 42 > 43 , 53 , 55 ' 60, 61, 62, 63, 65, 73 > 14 [, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 1 06, 108, 109, 110, 113 '114' 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 13 8 , 139 , 147 , 148 , 150 , 15 1 , 152 , 1 53 > 154, 15 5, 1 56 , 16 1 , 162 , 16 4 , 166 , 167 , 16 8 , 169 , 170 , 171 , 172 , 173 , 1 74 , 175 , 176 , 177 '179 ' 180 , 201042378 181 , 182 Further, 185, 187, 188, 193, 194, 199, 213 or 2 Further, these yellow pigments may be used singly or in combination of two or more to form a yellow photosensitive coloring composition of a yellow filter segment. As a red photosensitive coloring composition which can be used together with a red pigment, it is possible to use, for example, C.I. Pigment Orange 36, 43, 51, 55, 61, 71 or 73. Further, these orange pigments may be used singly or in combination of two or more kinds to form an orange photosensitive coloring composition of the orange filter segment. 0 In the green photosensitive coloring matter for forming the green filter segment, for example, C.I. Pigment Green 7, 7, 36, 37, and 58 color pigments can be used. In the green photosensitive coloring composition, in addition to the green pigment, the above yellow pigment may be used in combination. ' In the blue photosensitive coloring for forming the blue filter section, for example, C. I · Pigment Blue 1 5, 1 5 : 1, 1 5 : 2, 1 5 : 3, 1 15 can be used. : Blue pigments of 6, 16, 22, 60, 64, and 80. In the blue coloring composition, in addition to the blue pigment, a violet material such as C.I. Pigment Violet q 19, 23, 27, 29, 30, 32, 37, 40, 42 and 50 may be used in combination. In the cyan blue coloring composition for forming a cyan color filter segment, for example, C. I. Pigment Blue 1 5 : 1, 1 ί 15:3, 15:4, 15: Blue pigments of 6, 16 and 80. In the magenta photosensitive composition for forming the magenta filter segment, for example, a purple pigment such as C.I. Pigment Violet 1 and 19, and Pigment Red 81, 144, 146, 177, and 169 can be used. Red pigment. In the color-sensitive coloring composition, in addition to the purple pigment and the orange color of the yellow pigment, the composition is 5:4, and the light color is 1' color color 1:2> The magenta material may be used in addition to -10-201042378, and the above yellow pigment may be used in combination. In the black photosensitive coloring composition for forming a black matrix, for example, carbon black, aniline black, an anthraquinone black pigment or an anthraquinone black pigment can be used. Specifically, for example, c · I · pigment black 1, 6, can be used. 7, 1, 2, 0 or 3 1. A mixture of red pigment, blue pigment and green pigment is also used for the photosensitive coloring composition in black. As a black pigment, carbon black is preferred from the viewpoint of price and shielding. Carbon black can also be surface treated with a resin or the like. Further, in order to adjust the color tone, a blue 0 color pigment or a purple pigment may be further used in the black photosensitive coloring composition. From the viewpoint of the shape of the black matrix, carbon black preferably has a specific surface area in the range of 50 to 200 m 2 /g in accordance with the BET (Brunauer-Emmett-Teller) method. When 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 larger surface area is used, since the dispersing aid is excessively adsorbed to the carbon black, it is necessary to increase the amount of the necessary dispersing aid in order to exhibit various physical properties. Further, from the viewpoint of sensitivity, carbon black is preferably used in an amount of 120 ml/100 g or less in dibutyl phthalate (hereinafter referred to as Q "DBP"), and preferably in a smaller amount of DBP. The average primary particle diameter of the carbon black is preferably in the range of 20 to 50 nm. Carbon black having a small average primary particle size may be difficult to disperse at a high concentration, and it is difficult to obtain a black photosensitive coloring group and a good product with good stability over time. On the other hand, when carbon black having a large average primary particle diameter is used, the shape of the black matrix may be deteriorated. Further, examples of the inorganic pigment include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, -11-201042378 ultramarine blue, indigo, and chromium oxide. Metal oxide powder, metal sulfide powder and metal powder of green 'cobalt green, amber, titanium black, synthetic iron black, titanium oxide and iron oxide. When an inorganic pigment is used, it is typically used in combination with an organic pigment in order to ensure good coatability, sensitivity, and development properties while maintaining saturation and brightness. In the photosensitive coloring composition described above, it is possible to contain a dye in a range in which the heat resistance is not lowered for the purpose of coloring. From the viewpoint of obtaining sufficient color reproducibility, the concentration of the pigment (A) of all the nonvolatile components of the photosensitive coloring composition is preferably 10% by weight or more, more preferably 15% by weight or more, and more preferably 20% by weight or more is preferred. Further, from the viewpoint of the stability of the photosensitive coloring composition, the concentration of the pigment (A) of the total nonvolatile component of the photosensitive coloring composition is preferably 90% by weight or less, and preferably 80% by weight or less. More preferably, it is preferably 70% by weight or less. - <Transparent Resin (B)> The transparent resin (B) contained in the photosensitive coloring composition is in the range of the total wavelength region of 400 to 700 nm, particularly in the total visible light region, The transmittance is preferably 80% or more, more preferably 95% or more. In the transparent resin (B), a thermoplastic resin, a thermosetting resin or a photosensitive resin can be used alone or in combination of two or more. Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyacetic acid. Vinyl ester, polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene, Polybutadiene and polyimine resin. -12- 201042378 The thermosetting resin may, for example, be an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, or the like. Phenolic resin. As the photosensitive resin, for example, a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an 'amino group, or a (meth) group having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group can be used. A resin obtained by reacting an acrylic acid compound or cinnamic acid with a photocrosslinkable group such as a (meth)acryl fluorenyl group or a styryl group in the linear polymer described above. Further, as the photosensitive resin, for example, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer can be used, by (meth) A (meth)acrylated half esterified product having a hydroxyl group such as a hydroxyalkyl acrylate. In addition, in the present specification, when a compound is labeled with "(meth). propylene group", the compound means a compound which can read "(meth)acrylyl" as "propenyl", and It is also possible to read "(meth)acryl group" as any of "methacryl" compounds. Further, in the present specification, when Q is labeled with "(meth)acryl oxime" for a certain functional group, the functional group means that "(meth)acryl oxime" can be read as a functional group of "acrylofluorene". And it is also possible to read "(meth) propylene oxime" as any one of the functional groups which are "methacryl oxime". Further, 'in the present specification, when a compound is labeled with "(meth) acrylate"), the compound means a compound which can read "(meth) acrylate" as "acrylate", and "(Meth) acrylate" is read as any of the "methacrylate" compounds. The transparent resin (Β) is used in an amount of, for example, 20 to 400 parts by weight, based on 1 part by weight of the pigment (Α), preferably in an amount of 50 to 250 parts by weight. -13-201042378 <Photopolymerizable Compound (c))> The photopolymerizable compound (C) is a photopolymerizable monomer or oligomer. As the photopolymerizable compound (C). The photopolymerizable compound (C) may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxy'ethyl (meth)acrylate or (meth)acrylic acid-2- Hydroxypropyl ester, cyclohexyl (meth)acrylate, cesium-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, neopentyltriol tri(meth)acrylate, 1 ,6-hexanediol diepoxypropyl ether di(meth)acrylate, bisphenol A diepoxypropyl ether di(meth)acrylate, neopentyl glycol diepoxypropyl ether di(a) Acrylate, dipentaerythritol hexa(meth) acrylate, tricyclodecyl (meth) acrylate, ester acrylate, methylol melamine (meth) acrylate, epoxy ( Various acrylates or methacrylates such as methyl) propylene esters and urethane acrylates; (meth)acrylic acid Styrene; vinyl acetate; hydroxyvinyl vinyl ether; ethylene glycol divinyl ether; neopentyl alcohol trivinyl ether; (meth) propylene oxime Q amine; N-hydroxymethyl (meth) acrylamide; N-vinylformamide, acrylonitrile, and the like. These may be used alone or in combination of two or more. The photopolymerizable compound (C) is used, for example, in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the pigment (A). <Photopolymerization Initiator (D)> The photopolymerization initiator (D) is, for example, a compound represented by the following formula (1) which is generally called an oxime ester. -14- 201042378 Equation (1):

In the formula (1), X1, X3 and X6 each independently represent R11, 0rm, COR11, SR11, CONR12R13 or CN. X2 represents an alkyl group having 1 to 20 carbon atoms which may have a substituted mercapto group, an aryl group having 6 to 30 carbon atoms which may have a substituent, and an aromatic group having 7 to 30 carbon atoms which may have a substituent. The alkyl group 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 aralkyl group having 7 to 30 carbon atoms which may also have a * substituent may mean that the methylene chain may also contain an unsaturated group. One or more of a bond, an ether bond, a thioether bond, an ester bond, a thioester bond, a guanamine bond, and a urethane bond, and may have a ring structure. X4 and X5 each independently represent R11, OR11, SR11, COR11, q CONR12R13 'NR12CORm ' OCOR11, COOR11, SCORn, COSR11, COSR11, CSOR11, CN, a halogen atom or a hydroxyl group, and R11, R12 and R13 are each independently represented. a hydrogen atom, 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 an aralkyl group having 7 to 30 carbon atoms which may have a substituent. 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 having a substituent and the aralkyl group having 7 to 30 carbon atoms which may have a substituent means that an unsaturated bond may be contained in the methylene chain. One or more of an ether bond, a thioether bond, an ester bond, a thioester bond, a guanamine bond, and an amine group A-15-201042378 acid ester bond, and may have a ring structure. The a and b systems each independently represent an integer of 〇3. X1 is methyl, ethyl, n-propyl, isopropyl, 'n-butyl, isobutyl, and the like from the viewpoints of ease of storage, sensitivity, solubility, and photosensitivity of the photosensitive coloring composition. An alkyl group having 10 or less carbon atoms such as a tributyl group, a n-pentyl group, an isopentyl group, a third pentyl group, an n-hexyl group or a 2-ethylhexyl group; and a cyclopentyl group and a cyclohexyl group having 10 or less carbon atoms; a cyclic alkyl group; or a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, a 2-(1-methoxypropyl) 0 group, and a 2-(1-ethoxy group) An alkyl group having 10 or less carbon atoms and having an ether bond in the methylene chain is particularly preferable. From the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability of the photosensitive coloring composition, X3 is hydrogen; methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, An alkyl group having 6 or less carbon atoms such as a third butyl group, an n-pentyl group, an isopentyl group, a 1,3-pentyl group or a n-hexyl group; a cyclic alkyl group having 6 carbon atoms such as a cyclopentyl group and a cyclohexyl group; Or the number of carbon atoms such as methoxymethyl, ethoxymethyl, ethoxyethyl, 2-(1-methoxypropyl) and 2-(1-ethoxypropyl Q) groups is An alkyl group having 6 or less and having an ether bond in the methylene chain is particularly preferred. From the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability of the photosensitive coloring composition, X2 and X6 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and An alkyl group having 6 or less carbon atoms such as a tributyl group, a n-pentyl group, an isopentyl group, a third pentyl group and a n-hexyl group; a cyclic alkyl group having 6 or less carbon atoms such as a cyclopentyl group and a cyclohexyl group; Or the number of carbon atoms such as methoxyethyl, ethoxymethyl, ethoxyethyl, 2-(1-methoxypropyl) and 2-(1-ethoxypropyl) are An alkyl group having 6 or less and having an ether bond of -16 to 201042378 in the methylene chain is particularly preferred. From the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability of photosensitive coloring compositions, X4 and X5 are hydrogen; or methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl An alkyl group having 6 or less carbon atoms such as a group, a tributyl group, a n-pentyl group, an isopentyl group, a third pentyl group and a n-hexyl group is particularly preferred. Preferred examples of the photopolymerization initiator represented by the above formula (1) include the following compounds. 〇

201042378

-18- 201042378

The method for synthesizing the photopolymerization initiator represented by the above formula (1) is not particularly limited to -19 to 201042378, and the following method can be utilized. <Step 1> Synthesis of steroids: In the presence of chlorination (AIC13) The nitroguanidine compound 1 is reacted with chlorochloride 2 to obtain the target substance, i.e., steroid 3. <Step 2> Synthesis of the compound represented by the formula (1): The steroid 3, hydroxylamine hydrochloride and dimethylformamide (DMF) were mixed, and the mixture was heated and stirred to obtain a hydrazine compound 4. Subsequently, the ruthenium compound (oxime ester) 4 and the acid anhydride 5 are heated and stirred to effect the reaction. After completion of the reaction, the mixture was neutralized with a base to obtain a photopolymerization initiator represented by the above formula (1).

-20- 201042378 oxime ester 4

By using the photopolymerization initiator (D) represented by the above formula (1), it is possible to obtain a photosensitive coloring composition which is excellent in image development resistance and excellent in production stability of a color filter. By using a photosensitive coloring composition containing the photopolymerization initiator, a high-quality filter segment and a black matrix can be formed. The photopolymerization initiator (D) represented by the above formula (1) is formed by cleavage of an ultraviolet ray and a N-0 bond of hydrazine to form an imine radical and an alkoxy radical. Since the radicals are further decomposed to generate a high activity free radical, a small amount of exposure can form a pattern. Further, 'the absorption wavelength in the range of 330 nm to 430 nm due to the nitro group-based sulfhydryl group' shows a high reaction effect in the broad wavelength range from the ultraviolet region to the visible region. Further, it is considered that the -c 6 Η 3 (X3) 〇 X2 portion of the above formula (1) improves the imaging resistance. The photopolymerization initiator (D) represented by the formula (1) is preferably used in an amount of 2 to 50 parts by weight, for example, in an amount of from 1 to 1% by weight, based on 1 part by weight of the pigment (?). By using the photopolymerization initiator (D)' shown by the above formula (1), it is possible to obtain a photosensitive coloring composition which is excellent in development resistance and can improve the production stability of the color filter. By using the photosensitive coloring composition containing the photopolymerization initiator - 21 - 201042378, a high-quality filter segment and a black matrix can be formed. As the photopolymerization initiator (D) ', a compound represented by the following formula (2) or (3) can be used. Equation (2):

Equation (3):

In the formulae (2) and (3), X1 to X4 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms. The photosensitive coloring composition containing the photopolymerization initiator (D) represented by the above formula (2) or (3) can be patterned with high sensitivity and high residual film ratio. Therefore, when such a photosensitive coloring composition is used, it is possible to improve the production stability of the color filter, and to form a filter segment and a black matrix of an excellent pattern shape. The photopolymerization initiator (D) represented by the above formula (2) or (3) is an oxime ester-based photopolymerization initiator. The urethane photopolymerization initiator generates an imine radical and an alkoxy radical by absorbing ultraviolet rays and cleaving the N-0 bond of hydrazine. Since the radicals such as -22-201042378 are further decomposed to generate highly reactive radicals, a small amount of exposure can form a pattern. The photopolymerization initiator (D) represented by the above formula (2) or (3) can be produced by using the ruthenium compound as a starting material in accordance with the following method. Such a method is also described in No. 3860170 or No. 3992725. For example, an oxazole compound is reacted with carboxyindole chloride in the presence of zinc chloride to give a hydrazine compound. Subsequently, the hydrazine compound is reacted with an alcohol compound in the presence of a third butyl ammonium hydrogenated diene sulfate to obtain a steroid. Subsequently, the steroid is reacted with hydroxylamine hydrochloride to obtain a hydrazine compound. Further, the photopolymerization initiator represented by the above formula (2) or (3) can be obtained by reacting the obtained hydrazine compound with an acid anhydride. The photopolymerization initiator (D) represented by the above formula (2) or (3) can be identified by elemental analysis of hydrazine and 1H-NMR (nuclear magnetic resonance). The photopolymerization initiator represented by the above formula (2) or (3) is used, for example, in an amount of from 1 to 200 parts by mass, preferably from 3 to 150 parts by weight, based on 100 parts by weight of the pigment (A). As the photopolymerization initiator (D), only one type of the compound represented by the above formulas (1) to (3) may be used, and two or more kinds of these compounds may be used. When one or more compounds represented by the formula (1) and one or more compounds represented by the formula (2) or (3) are used in combination, the pigment (A) is used in an amount of 1 part by weight. The total amount of the compound represented by any one of the above formulas (1) to (3) is, for example, in the range of 1 to 200 parts by weight, preferably 2 to 150 parts by weight. <Other polymerization initiator> The above-mentioned photosensitive coloring composition may be used in combination with other photopolymerization initiators in addition to the photopolymerization initiator (D) in the range of -23 to 201042378. As the additional photopolymerization initiator, for example, 4-phenoxydichloroacetamidine, 4-tert-butyl-dichloroacetamidine, diethoxyethylbenzene, and ι_(4-isopropyl) can be used. Phenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl' ketone, 2-methyl-1-[4-(methylthio)phenyl]-2 - Phenylpropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]4^4-(4-morpholinyl)phenyl]-1-butanone and Benzene benzene compound such as 2-phenyl-2-dimethylamino-1-(4-teranylphenyl)-butylidene-1-one; benzoin, benzoin methyl ether, benzoin a benzoin compound such as ethyl ether, benzoin 0 propyl propyl ether and benzoin methyl ketal; diphenyl ketone, benzhydryl benzoic acid, methyl benzyl benzoyl benzoate, 4_ Phenyldiphenyl ketone 'hydroxydiphenyl ketone, acrylated diphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide and 3,3',4,4'-tetra a diphenyl ketone compound such as 4-butylperoxycarbonyl)diphenyl ketone; thioxanthone, 2 -chloro-9-oxopurine, 2 -methyl -9-oxysulfide Dill喔, isopropyl-9-oxysulfide 9-oxosulfonium oxime compounds such as star, 2,4-diisopropyl-9-oxosulfonium and 2,4-ethyl-9-oxosulfanthine; 2,4, 6-trichloro-s-tripper '2-phenyl-4,6-q bis(trichloromethyl)-s-three-plow, 2-(p-methoxyphenyl)-4,6-double ( Trichloromethyl)-s-tripper, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-three tillage, 2_sunflower-4,6-bis(trichloromethane) Base)-S-three tillage, 2,4-bis(trichloromethyl)-6-styryl-s-three tillage, 2-(naphtho-1-yl)-4,6-bis(trichloro) Methyl)-s-triterpene, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-3_triterpene, 2,4-trichloromethyl Triterpenoids such as benzyl-(sunnyl)-6-triad and 2,4-trichloromethyl(4,-methoxystyryl)-6-triterpene; 1,2-octanedione -i-[4-(phenylthio K-)-, 2-(0-benzhydryl)] and 〇-(ethinyl)-fluorene-fluorene-phenyl-2-oxoxy-2-( An oxime ester compound such as 4-methoxy-naphthyl)ethylene)hydroxylamine; and a phosphine-based compound such as bis-24-201042378 (2,4,6-trimethylbenzylidene)phenylphosphine; 9,10-phenanthrene compounds such as phenanthrenequinone, camphorquinone and ethylhydrazine Borate ester; yesterday azole compound; imidazole compound; titanocene-based compound, or the like. These additional photopolymerization initiators may be used alone or in combination of two or more kinds at any ratio as necessary. As a particularly preferable photopolymerization initiator, for example, an α-aminoalkyl acetonitrile benzene photopolymerization initiator can be mentioned. As the α-aminoalkyl acetonitrile-based photopolymerization initiator, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-zolinol propane-1-Q ketone, 2- Benzyl-2-dimethylamino-1-(4-morpholinyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl ]-1-[4-(4-tyrosolinyl)phenyl]-butanone or a mixture of two or more of these. The use of such a photopolymerization initiator is advantageous in that a color filter having no wrinkles on the surface of the coating film is obtained. When the compound represented by the above formula (1) is used as the photopolymerization initiator (D), the additional photopolymerization initiator is added to 100 parts by weight of the photopolymerization initiator (D) represented by the formula (1). It is used, for example, in an amount of 5 to 25 parts by weight, more preferably 10 to 20 parts by weight. When the compound represented by the above formula (2) or (3) is used as the photopolymerization initiator (D), the above-mentioned addition is carried out with respect to 1 part by weight of the photopolymerization initiator (D) represented by the formula (1). The photopolymerization initiator is used, for example, in an amount of from 1 to 200 parts by weight, preferably from 3 to 150 parts by weight. <Sensitizer> The photosensitive coloring composition described above may further contain a sensitizer. When the compound of the above formula (1) is used as the photopolymerization initiator (D), the sensitizer (Ε)-25-201042378 can be used, for example, with respect to 1 part by weight of the photopolymerization initiator (D). It is used in an amount of from 0 to 60 parts by weight. When the compound represented by the above formula (2) or (3) is used as the photopolymerization initiator (D), the sensitizer (E) can be, for example, 1 part by weight based on 1 part by weight of the photopolymerization initiator (D). It is used in an amount of 1 to 1 part by weight. 'As the sensitizer (E), for example, unsaturated ketones represented by chalcone derivatives and dibenzylideneacetone; and 1,2-di which are represented by benzoin and camphorquinone Ketone derivatives; benzoin derivatives; anthracene derivatives; naphthoquinonediazide derivatives; anthracene derivatives; xanthene derivatives; ^ thioxanthene derivatives; Xanthone derivative; 9-oxoththene; coumarin derivative; ketocoumarin derivative; anthocyanin derivative; merocyanin derivative; Polymethine pigments such as oxonol derivatives; acridine derivatives; hydrazine trap derivatives; thiatene derivatives; hydrazine trap derivatives; indole derivatives; anthracene derivatives; azulenium derivatives Squarylium derivative; porphyrin derivative; tetraphenylporphyrin derivative; triarylmethane derivative; tetrabenzoporphyrin derivative; tetrapyrrolidine tetraazaporphyrin derivative : phthalocyanine derivative Q; tetraoxatetraazaporphyrin derivative; tetraquinoxalinyl porphyrazine derivative; naphthoquinone blue Biological; subphthalocyanine derivative; pyranyl derivative; thiapyran derivative; tetraporphyrin derivative; annulene derivative; spiropyran derivative; Thiopyran derivatives; metal aromatic hydrocarbon complexes: organic ruthenium complexes; and mischidone derivatives. In addition, as a specific example of the sensitizer (E), the "Chemicals of Functional Colors" (1981, CMC), which is edited in the "Handbook of Colors" (1986, Kodansha), and Okawahara, etc. The sensitizer described in "Special Functional Materials" (1 986, CMC), ed., and the sensitizer (E) are not limited to these. Further, the composition may further contain a sensitizer that absorbs light from the ultraviolet to the near-infrared region. Among the sensitizers (E), a sensitizer which is particularly suitable for sensitizing the photopolymerization initiator (D) represented by the formula (1), for example, a 9-oxopurine derivative can be mentioned. And Michelin derivatives. More specifically, for example, 2,4-diethyl-9-oxosulfonium, 2 chloro-9-oxosulfonate, 2,4-dichloro-9-oxosulfonium, 2 -isopropyl-9-oxosulfonium ill, 4-isopropyl-9-oxosulfonium [1|comet, 1-chloro-4-phenoxymethyl-9-oxosulfide Bill, 4, 4'-bis(dimethylamino)diphenyl ketone, 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis(ethylmethylamino)diphenyl ketone, N-ethylcarbazole, 3-benzylidene-N-ethylcarbazole and 3,6-diphenylmethylhydrazine-N-ethyl oxime sensitizer (E) can also be contained in any ratio. Two or more sensitizers. When the compound represented by the formula (1) is used as the photopolymerization initiator (D), the weight Ia of the photopolymerization initiator (D) and the weight of the photopolymerizable compound (C) are in the photosensitive coloring composition. The ratio Ia/Μ is preferably 0.05 to 0.50, 〇 is preferably 0.05 to 0.25, and particularly preferably 0.10 to 0.20. In addition, when the compound represented by the formula (1) is used as the photopolymerization initiator (D), the photopolymerization initiator (D) and the sensitizer (Ε) when the photosensitive coloring composition contains a sensitizer (Ε) The ratio Ib/M of the total weight Ib to the weight 光 of the photopolymerizable compound (C) is preferably from 0_1 Å to 0.60, more preferably from 0.1 Å to 0.37, and particularly preferably from 0.12 to 0.30.

When the Ia/M ratio or the Ib/M ratio is small, it is difficult to achieve high imaging tolerance. When the Ia/M ratio or the Ib/M ratio is large, it is difficult to achieve an excellent pattern shape. When the compound represented by the formula (2) or (3) is used as a photopolymerization initiator (D) -27 to 201042378, the photosensitive resin composition, the weight P of the transparent resin (B), and the photopolymerizable compound (C) The weight ratio Μ/P is preferably 0.10 to 0.60, more preferably 0_10 to 0.50, and particularly preferably 0.20 to 0.50. It is difficult to achieve high sensitivity in cases where the Μ/P ratio is small. When the Μ/P ratio is large, it is difficult to form a straight line. 'Excellent pattern, and it is easy to cause problems such as stickiness. When the compound represented by the formula (2) or (3) is used as the photopolymerization initiator (D), the ratio of the weight Ia of the photopolymerization initiator (D) to the weight 前述 of the photopolymerizable compound (C) Ia/M is preferably from 0.05 to 0.25, more preferably from 0.10 to 0.25, and particularly preferably from 0.15 to 0.25. In addition, when the compound represented by the formula (2) or (3) is used as the photopolymerization initiator (D), photopolymerization is carried out in the photosensitive coloring composition, and the photosensitive coloring composition contains a sensitizer (Ε). The ratio Ib/M of the total weight Ib of the initiator (D) to the sensitizer (Ε) to the weight of the photopolymerizable compound (C) is preferably from 0.10 to 0.40, preferably from 15 to 0.37. It is particularly good at 0.22 to 0.37.

It is difficult to achieve high sensitivity in the case where the Ia/M ratio or the Ib/M ratio is small. When the Ia/M ratio or the U/M ratio is large, it is difficult to form a pattern having excellent linearity. Q &lt;Polyfunctional thiol (F)&gt; The photosensitive coloring composition described above preferably further contains a polyfunctional thiol (F). The polyfunctional thiol (F) may have two or more thiol groups (SH). When used together with the above photopolymerization initiator (D), the polyfunctional thiol (F). The radical polymerization process after light irradiation acts as a chain transfer agent, which is less susceptible to oxygen-induced polymerization inhibition. Thiyl radical. Therefore, when the polyfunctional thiol (F) is further contained, the sensitivity of the photosensitive coloring composition becomes higher. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as a methylene group and a methyl group -28-201042378 is preferred. Examples of the polyfunctional aliphatic thiol bonded to the aliphatic group include hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, and 1,4-butane. Alcohol dithioglycolate, ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trishydroxymethyl propane thioglycolate, trimethylolpropane thiopropionate, trihydroxyl Methylpropane ginseng (3-hydrothiobutyrate), pentaerythritol thioglycolate, pentaerythritol thiopropionate, trihydrothiopropionic acid ginseng (2-hydroxyethyl) Cyanurate, 1,4-dimethylhydrothiobenzene, 2,4,6-trihydrothio-s-tripty 4 and 0 2-(N,N-dibutylamino)-4 , 6-dihydrothio-s-three school 4 and so on. Among these, ethylene glycol dithiopropionate, trimethylolpropane thiopropionate and neopentyl sulfonium thiopropionate are preferred. These polyfunctional thiols may be used singly or in combination of two or more. The content of the polyfunctional thiol (F) is determined in such a manner that the effect as a chain transfer agent can be sufficiently exhibited without impairing the developability and adhesion. The content of the polyfunctional thiol (F) is preferably from 0.05 to 100 parts by weight, more preferably from 1.0 to 50.0 parts by weight, per 100 parts by weight of the pigment (A). &lt;Solvent&gt; The photosensitive coloring composition described above may contain a solvent. When a solvent is used, it is 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, a coating film can be easily formed on a transparent substrate such as a glass substrate to have a dry film thickness of 22 to 10/zm. A filter segment or a black matrix can be easily formed. The solvent may, for example, be 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butanediol, 1,3-butanediol diacetate or 1,4-dioxane. Alkane, 2-heptanone, -29- 201042378 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethyl Cyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxyacetic acid -3-methylbutyl ester, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-di Methylacetamide, hydrazine, hydrazine-dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, hydrazine-methylpyrrolidone, o-xylene, o-chlorobenzene, o-diethylbenzene , o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, second butylene, tert-butylbenzene, r-butyrolactone, isobutanol, isophorone, ethylene glycol diethyl ether, B Diol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl Ether, ethylene glycol monobutyl ether acetate, ethylene glycol Propyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethyl diol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, - diethylene Alcohol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, two Ethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, Q dipropylene glycol monomethyl ether, dipropylene glycol monomethyl 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 isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, acetic acid Butyl ester, propyl acetate and dibasic acid ester. These can be used alone or in combination -30- 201042378. &lt;Other components&gt; In order to stabilize the viscosity of the composition over time, the photosensitive coloring composition may further contain a storage stabilizer. Further, in order to improve the adhesion to the transparent substrate, the photosensitive coloring composition may further contain an adhesion promoter such as a decane coupling agent. Examples of the storage stabilizer include a grade 4 surface chlorine such as benzyltrimethyl chloride or diethylhydroxylamine; an organic acid such as lactic acid or oxalic acid; a 0 methyl ether of the organic acid; and a third butyl tea. An organic phosphine such as phenol, tetraethylphosphine or tetraphenylphosphine; and a phosphite. Examples of the decane coupling agent include vinyl decane such as vinyl ginate (/3-methoxyethoxy) decane, vinyl ethoxy decane, and vinyl methoxy decane; r-methyl propylene oxime; (methyl-)propenyl decane such as oxypropyltrimethoxydecane; /3 -(3,4-epoxycyclohexyl)ethyltrimethoxydecane, /3 -(3,4-ring Oxycyclohexyl)methyltrimethoxydecane, /3-(3,4-epoxycyclohexyl)ethyltriethoxydecane, yS-(3,4-epoxycyclohexyl)methylqyl Epoxy decanes such as triethoxy decane, r-glycidoxytrimethoxydecane and τ-glycidoxytriethoxydecane; N-/3 (aminoethyl) 7-amine Propyltrimethoxydecane, N-/3 (aminoethyl)r-aminopropyltriethoxydecane, N-lu (amineethyl)r-aminopropylmethyldiethoxydecane, r- Aminopropyltriethoxydecane, r-aminopropyltrimethoxydecane, N-phenyl-r-aminopropyl.trimethoxydecane, and N-phenyl-r-aminopropyltriethoxy Amino decanes such as decane; and r-hydrothiopropyltrimethoxydecane and r-hydrothiopropyltriethoxy Alkyl sulfur silicon and other alkanes. The decane coupling agent is used, for example, in an amount of from 0.1 to 31 to 201042378 to 10 parts by weight, preferably from 0.05 to 5 parts by weight, based on 1 part by weight of the pigment (a). The photosensitive coloring composition described above may further contain an amine compound having an action of reducing dissolved oxygen. Examples of such an amine-based compound include triethanolamine, methylbisethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4- Isoamyl dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate and N,N-dimethyl-p-toluidine. 〇 &lt;Preparation of photosensitive coloring composition&gt; The photosensitive coloring composition is produced, for example, by the following method. First, the pigment (A) is dispersed in a transparent resin (B) and/or a solvent using various dispersing means to prepare a pigment dispersion. Examples of the dispersing means include, for example, a three-roll mill, a two-roll mill, a sand mill, a kneader, and a vertical ball mill. - Subsequently, in the pigment dispersion, the transparent resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D) are mixed with the sensitizer (E) and the polyfunctional thiol (F) as the case may be. , solvent and other ingredients, and stir the mixture. Thereby, 感光 a photosensitive coloring composition can be obtained. Further, the photosensitive coloring composition containing two or more kinds of pigments can be mixed, for example, by mixing a plurality of pigment dispersions in which the pigments are finely dispersed in the transparent resin (B) and/or a solvent, and Further, the photopolymerization initiator (D), the photopolymerizable compound (C), and the like are mixed in the mixture and stirred. - When the pigment is dispersed in the transparent resin (B) and/or the solvent, a dispersing aid such as a resin type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. The dispersing aid is excellent in dispersing the pigment and has a large effect of preventing re-agglomeration of the pigment after dispersion. Therefore, when a photosensitive coloring composition comprising a pigment-B-32-201042378 material dispersed in a transparent resin (B) and/or a solvent using a dispersing aid is used, a color filter excellent in light transmittance can be easily obtained. . The dispersing aid is used, for example, in an amount of from 1 to 40 parts by weight, preferably from 0.1 to 30 parts by weight, per 100 parts by weight of the pigment (A). The resin type pigment dispersant is a resin which adsorbs to a pigment and has a function of dispersing a pigment in a pigment carrier, and has a pigment affinity site adsorbed to the pigment and a site compatible with the dye carrier. As the resin type pigment dispersant, for example, a polycarboxylate such as a polyurethane; a polyacrylic acid oxalate; an unsaturated polyamine; a polycarboxylic acid; a polycarboxylic acid (partial) amine salt; a polycarboxylate can be used. Ammonium salt; polycarboxyalkylamine salt; polyoxyalkylene; long chain polyamine phthalamide phosphate; hydroxyl group-containing polycarboxylate; such modified; poly(lower alkylene imine) An oily dispersant formed by reacting a polyester having a free carboxyl group and an oily dispersant such as the salt; (meth)acrylic acid-styrene copolymer; - (meth)acrylic acid-(meth)acrylate copolymer Styrene-maleic acid copolymer; water-soluble resin or water-soluble polymer compound such as polyvinyl alcohol and polyvinylpyrrolidone; polyester; modified polyacrylate; ethylene oxide / Q a propylene oxide addition compound; or a phosphate ester. These may be used alone or in combination of two or more. As a commercially available resin type pigment dispersing agent, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, which are manufactured by BYK-Chemie Co., Ltd., may be mentioned. 165, 166, 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-3 000, 9000, 1 3240, -33- 201042378 13650, 13940, 17000, 18000, 20000, 21000, 24000' 26000, 27000, 28000, 31845, 32000, 32500, manufactured by LUBRIZOL, Japan. 32600, 34750, 36600, 3 8 5 00, 41 000, 4 1 090 and 53 095, etc.; and EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050 'LP4055, 400, manufactured by EFKA Chemicals. 401 &gt; 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like. The surfactant may, for example, be a polyoxyethylene alkyl ether sulfate, a sodium dodecylbenzenesulfonate, an alkali salt of a styrene-acrylic acid copolymer, an alkyl alkane naphthalenesulfonate or an alkyl diphenyl group. Sodium ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer and poly An anionic interface active agent such as oxyethylene alkyl ether phosphate; polyoxyethylene oil decyl ether, polyoxyethylene lauryl ether, polyoxyethylene fluorenyl phenyl ether, polyoxyethylene alkyl ether phosphate; a nonionic surfactant such as polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; a cation of an alkyl 4-grade ammonium salt and such an ethylene oxide adduct A Q-surfactant; and an amphoteric surfactant such as an alkylbetaine such as an alkyldimethylaminoacetic acid betaine or an alkylimidazole. These may be used alone or in combination of two or more. A pigment derivative is a compound in which a substituent is introduced into an organic pigment. The organic pigment also contains a pale yellow aromatic polycyclic compound such as a naphthalene or an anthracene which is not generally called a pigment. For example, JP-A-63-305173, JP-A-57-15620, JP-A-5-9-40 1 72, and JP-A-63-117/01 The person stated in the Gazette No. 5-9469. These may be used alone or in combination of two or more and -34- 201042378. The coarse particles of 5 vm or more, preferably coarse particles of 1 vm or more, more preferably coarse particles of 5 vm or more, are removed from the photosensitive colored composition by means of centrifugation, a sintered filter, a membrane filter, or the like. And the dust mixed into &quot; is better. The above-mentioned photosensitive coloring composition can be prepared in the form of a solvent developing type or an alkali developing type colored resist. The colored resist material is, for example, a dispersion of the pigment (A) in a composition containing a transparent resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent. . &lt;Color Filter&gt; Subsequently, a color filter of one embodiment of the present invention will be described. A color filter according to one aspect of the present invention includes a filter segment or a black matrix formed of 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 filter segment, at least one green A blue Q (cyan color) filter segment and at least one yellow filter segment. As the transparent substrate, for example, a glass plate such as soda lime glass, low alkali borosilicate glass, and alkali-free aluminoborosilicate glass; or polycarbonate, polymethyl methacrylate, and polyethylene terephthalate can be used. Resin board. When the liquid crystal display device is used, a transparent electrode made of indium oxide and tin oxide may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal molecules after the panel. The dry film thickness of the filter segments and the black matrix is preferably from 0.2 to 10/im, more preferably from 2 to 5 // m. For the drying of the coating film, for example, a -35-201042378 pressure dryer, a convection oven, an IR (infrared ray) oven or a hot plate can be used. u The filter segments and the black matrix are formed in accordance with the photolithography method, for example, according to the following method. The photosensitive coloring composition which is prepared as a solvent developing type or an alkali developing type colored resist material is applied to a transparent substrate so as to have a dry film thickness of, for example, 0.2 to 10 # m. The coating method using spray coating, spin coating, slit coating, roll coating, or the like is applied to the colored resist. 0 After the coating film is dried as necessary, a mask having a predetermined pattern is placed in contact with or in contact with the coating film, and light such as ultraviolet rays is irradiated through the mask. This light source is, for example, a mercury lamp. Instead of performing a laser beam exposure on the film, instead of using a reticle. Laser systems such as • use laser beams with an output wavelength of 300 to 410 nm. Laser can be used. Solid-state laser including semiconductor laser; YAG (yttrium-aluminum-garnet; yttrium-aluminum-garnet) laser; and argon laser, krypton laser, carbon dioxide gas laser and excimer A laser known to the public of a gas laser such as a laser. The exposed portion of the coating film is hardened by exposure using the mask or laser beam drawing. Subsequently, the coating film is immersed in a solvent or an alkaline developing solution, or the developing solution is sprayed onto the coating film to remove the uncured portion, i.e., the unexposed portion, from the coating film. As the alkaline developing solution, for example, an aqueous solution of sodium carbonate or sodium hydroxide or an organic base such as dimethylbenzylamine or triethanolamine can be used. In the developing solution, an antifoaming agent and a surfactant may also be added. The development processing method is, for example, 'a spray imaging method, a spray imaging method, an immersion imaging method, or a puddle development method. -36- 201042378 Subsequently, the pattern obtained by development was applied as needed to promote heating of the polymerization reaction. The respective sections of the filter section and the black matrix can be obtained in this way. According to the photolithography method, the filter segments and the black matrix can be formed with higher precision than the printing method. Further, after drying the coating film, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied to the coating film and dried before the exposure of the coating film. A coating film composed of a water-soluble or alkali-soluble resin is used to prevent oxygen from blocking polymerization during exposure. Therefore, when the coating film is formed, the sensitivity of the coating film composed of the photosensitive coloring composition to the exposure light can be improved. Hereinafter, examples of the invention will be described. Further, the embodiments are intended to be used to understand and practice the invention, and it is understood that they are not intended to limit the scope of the invention. In addition, in the examples and comparative examples, "parts" means "parts by weight". <<Test Example 1 First, the Q-switching system of the acrylic resin solution used in Test Example 1 will be described. Further, the molecular weight of the resin described below is a weight average molecular weight converted to polystyrene in terms of GPC (gel permeation chromatograph). Specifically, the molecular weight of the resin described below is HLC-8220GPC (manufactured by TOSOH Co., Ltd.) manufactured by TOSOH Co., Ltd., and TSK-GEL &gt; SUPER HZM-N is used as a column in two strings, and The weight average molecular weight converted to polystyrene measured using THF (tetrahydrofuran) as a solvent. [Preparation of Acrylic Resin Solution] 3 70 parts of cyclohexanone was injected into the reaction vessel and heated to 80 ° C while nitrogen gas was introduced into the reaction vessel to -37 - 201042378. At this temperature, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl acrylate, 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2 were dropped into the reaction vessel over 1 hour. , a mixture of 2' azobisisobutyronitrile to cause polymerization. After the completion of the dropwise addition, it was allowed to stand at a temperature of 80 ° C for 3 hours. Subsequently, in the liquid, 1.0 part of azobisisobutyronitrile was added to 50 parts of cyclohexanone. The acrylic resin solution was obtained by keeping the liquid at 8 (the temperature of TC was allowed to stand for 1 hour). 0 After the acrylic resin was cooled to room temperature, it was sampled by about 2 g, and it was placed at The non-volatile matter was measured by heating at a temperature of 80 ° C for 20 minutes. Using the results of the measurement, cyclohexanone was added in such a manner that the previously synthesized acrylic resin solution had a nonvolatile content of 20% by weight. The obtained acrylic resin' The weight average molecular weight is 40,000. - [Preparation of Pigment Dispersion] The pigment, the resin type pigment dispersant, the pigment derivative, the acrylic resin, and the solvent are weights as indicated by the column labeled "p R" in Table 1 below. Ratio Q was uniformly mixed by stirring. Subsequently, the mixture was supplied to a sand mill by using a sand mill having a diameter of 1 mm for 5 hours, and further filtered using a filter. The liquid removes coarse particles of 5/czm or more, thereby obtaining a red pigment dispersion PR. In addition to the pigment, the resin type pigment dispersant, the pigment derivative, the acrylic resin, and the solvent, The green pigment dispersion PG was prepared by the same method as described in the red pigment dispersion p R except that the weight ratios shown in the columns of "PG", "PB" and "PBK" are shown in Table 1. Blue pigment dispersion PB and black pigment dispersion pbk. -38- 201042378 [Table 1] Pigment dispersion PR PG PB PBK PR254 6.82 PR177 1.08 PG36 8.93 PY150 0.88 2.74 PB15:6 12.88 CB 11.67 Resin type pigment dispersion 1.74 2.80 5.62 2.80 Pigment Derivatives 2.05 Acrylic Resin 5.83 5.53 1.50 5.53 Solvent 81.60 80.00 80.00 80.00 Total 100.00 100.00 100.00 100.00 In Table 1, the substance indicated by abbreviated or general name is specifically as follows. PR254 : Diketopyrrolopyrrole Pigment (C · I · Pigment Red 2 5 4) ("IRGAPHOR RED B-CF" by CIBA JAPAN Co., Ltd.) PR177 : 蒽醌-based pigment (CI Pigment Red 177) ("CROMOPHTAL RED A2B" by CIBA JAPAN Co., Ltd.) PG36 : Copper phthalocyanine pigment (CI Pigment Green 36) ("Li〇n〇lgreen6yk" manufactured by Toyo Ink Manufacturing Co., Ltd.) PY150 : Nickel azo complex compound (CI. Pigment Yellow i5〇) (E4g -39- 201042378 PB 1 5 :6 : ε-type copper phthalocyanine pigment (C.I_Pigment Blue 15:6) manufactured by LANXESS Co., Ltd. ("HELIOGEN BLUE-" manufactured by BASF Corporation L-6 7 00 F") CB : Carbon black (CI Pigment Black 7) ("MA11" manufactured by Mitsubishi Chemical Corporation) Resin pigment dispersant: "SOLSPERSE 2000" manufactured by LUBRIZOL Co., Ltd., Japan) Pigment Derivative: The following formula (4) The diketopyrrolopyrrole pigment derivative (4):

Acrylic resin solution: Acrylic resin solution prepared as before: Organic solvent: Cyclohexanone [Preparation of photosensitive coloring composition] The materials of the photosensitive coloring composition were mixed at a ratio (weight ratio) shown in Table 2. After sufficiently stirring, filtration was carried out to remove coarse particles having a diameter of 1 M or more from the dispersion. As described above, the photosensitive coloring compositions RR1 to RR19, RG1 to RG9, RBI, RB2, RBK1, and RBK2 are modulated. -40- 201042378 Ο ο

tN« 1 RR16 1 I 49.9 I CO ON I 0.20 I 1 0.05 1 1 2.07 1 38.5 1 loo.o 1 0.10 1 0.12 i LRR15 I 49.9 IV〇υ-ΐ L 1.00 J ! 2.07 1 41.5 1 loo.o 1 0.48 1 1 RR14 羑I 49.9 I ΟΟ "2.07 I 42.1 1 loo.o 1 0.56 1 1 RR13 g I 49.9 I rH ο L〇,〇9J 1 2.07 | 37.8 1 loo.o 1 0.04 1 1 RR12 I 49.9 I σ\ α; 1 0.13 1 [2.07 1 38.0 1 loo.o 1 0.06 1 1 RR11 £ I 49.9 I σ; 1 0.20 1 1 0.04 1 1 2.07 1 :38.3 1 , loo.o 1 i 0.12 1 1 RR10 £ Γ 49.9 I Ηη σ&lt; 1 0.20 1 1 0.04 1 1 2.07 1 CO CO loo.o 1 0.12 1 1 RR9 g I 49.9 I σ&lt; Γ 0.20 1 1 0.06 1 1 2.07 1 cn od CO :loo.o 1 1 0.13 1 1 RR8 g Γ 49.9 I νη σ&lt; 1 0.20 1 1 ).04 1 1 2.07 I 1 38.3 1 1 loo.o 1 1 0.12 I 1 RR7 g I 49.9 I cK 1 0.20 1 1 0.04 1 1 2.07 1 38.3 1 loo.o 1 0.12 1 RR6 .1 £ I 49.9 I σ&lt; 1 0.20 1 ! 0.04 1 1 2.07 1 38.3 1 loo.o 1 0.12 1 L RR5 JI 49.9 I Ό σ&lt; 1 0.20 1 丨2.07 1 cn od cn 1 100.0 1 1 0.10 1 I RR4 g I 49.9 I ν〇σ&lt; 0.20J 1 2.07 1 38.3 i 100.0 1 0.10 1 I RR3 I g I 49.9 I σ&lt; 1 0.20 I 1 2.07 1 CO od cn 1 100.0 1 ! 0.10 1 I RR2 g I 49.9 J VO cK I 0.20" ! 2.07 I 1 38.3 1 1 100.0 1 ! o.io I 1 RR1 g I 49,9 I VO σ&lt; I 0.20 I :2.07 I CO od CO i 100.0 I ί 0.10 I - I 1g ig Φ 槲m dance i llrnl P medicine m $ charm »&lt;-s 幽i)ml ipt Nw· difficult φ! factory firewood m gg spirit m « κ 挞•ίΒΕ ¢0 m net nr&gt;&lt;in m micro &lt;in hm An &gt; micro φ associated ISl micro HF &lt;nm micro an &lt;no W micro nr&gt; Φ age 0i m micro An condensed 瘁 4n 1 embedded Jilo &lt;ni QQ

1 RBK2 1 \ PBK I 1 49.3 1 3 CO 0.40 1 1 0.06 1 2.25 1 41.3 1 100.0 1 0.18 1 0.20 1 1 RBK1 I PBK | 丨49.3 1 5 cn c&gt; 1 0.40 1 1 0.06 1 2.25 | 41.3 1 loo. o 1 0.18 I 0.20 1 1 RB2 s 1 31.6 1 2 (Τ) ο ϊ—1 1 0.06 1 7.73 1 53.3 1 loo.o 1 0.13 I 0.14 1 1 RBI s 1 31.6 1 ι··Η VO CO 1 l. Oo 1 1 0.06 1 :7.73 1 i 53.3 1 ^ 100.0 1 :0.13 1 :0.14 1 1 RG9 s 1 49.3 Ό VO CO 0.22 Ί 1 0.06 1 &lt;N cs 41.3 1 loo.o 1 o.io 1 0.12 1 1 RG8 is 1 49.3 1 cn 1 0.22 1 1 0.06 1 v〇CS 41.3 1 loo.o 1 o.io 1 0.12 I 1 RG7 1 2 49.3 ON vd 1 0.22 1 ,0.06 1 2.25 1 41.3 1 100.0 1 o.io 1 0.12 I 1 RG6 I 2 1 49.3 1 〇〇oi 〇1—Η cs 44.6 1 loo.o 1 0.49 I 1 RG5 i 2 49-3 r—H CN ν〇cs • Η 2.25 1 1 45.2 1 ;100.0 1 0.56 1 1 RG4 2 1 49.3 1 〇〇[o.io 1 2.25 1 40.6 1 loo.o 1 0.04 1 1 1 RG3 1 2 1 49.3 1 1 0.14 1 2-25 | 1 40.8 1 i loo.o 1 1 0.06 1 1 1 RG2 S 丨49.3 CN 1 0.22 1 2.25 1 1 &lt; 1 100.0 1 0.10 1 1 1 RG1 2 1 49.3 1 04 1 0.22 1 2.25 | 41.1 1 i 100.0 1 1 0.10 1 1 1 RR19 £ 1 49.9 1 § cn 1 0.20 1 1 0.05 1 2.07 1 ΙΤϊ od cn 100.0 J _ai〇J 0.12 I 1 RR18 1 49.9 1 § cn I 0.20 1 1 0.05 I 2.07 I Wi οό CO 100ΌΙ 0.10 1 0.12 1 I RR17 g ON On cn 1 0.20 1 1 0.05 I 2.07 I wo od CO 100.0 I 0.10 I 0.12 IS' ε &gt;3 I IS Question ma m mi P 镳Φ 实 _ i1m1 Pi Φ Φ S: 塍m 黎 趣 B: &amp; grip · 4ππ mm mm &lt;n account m micro hm total nn &lt;! □ m &gt ; micro SF &lt;n Ν 激&lt;□ m Cl, micro&lt;ίπ m ο m hungry πη &lt;□ ffi microίί &lt;nm sea hit #! &lt;nem total i Q i Q _ I inch, 201042378 Table 2, the substance shown by the general name 'is specifically as follows. Pigment dispersion: ^ Previously prepared acrylic resin solution: 'Previously prepared acrylic resin solution Polyfunctional thiol: Trimethylolpropane trithiopropionate photopolymerization initiator W : 0 Light of formula (5) Polymerization Initiator Photopolymerization Initiator Y: Photopolymerization Initiator Photopolymerization Initiator T represented by Formula (6): Photopolymerization Initiator represented by Formula (7) - Photopolymerization Initiator V: Formula (8) Photopolymerization initiator photopolymerization initiator Z: q 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone-1-( 0-acetonitrile) (IRGACURE OXE02, manufactured by CIBA JAPAN Co., Ltd.) Photopolymerization initiator P: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-l-[4 -(4-tyrosolinyl)phenyl]-1-butanone ("IRGACURE 379", manufactured by CIBA JAPAN Co., Ltd.) Photopolymerization initiator Q: 2-methyl-1-[4-(methylthio)phenyl] -2 - porphyrin propan-1-one-42- 201042378 ("IRGACURE 907", manufactured by CIBA JAPAN Co., Ltd.) Photopolymerization initiator R: . 2,4,6-trimethylbenzylidene-diphenyl-oxidation Phosphine ("LUCIRIN TPO" manufactured by BASF Corporation) Sensitizer: 2,4 -_•Ethyl-9-oxosulfonate (曰本"KAYACURE DETX-S" manufactured by Pharmacy Co., Ltd.) Photopolymerizable compound: Epoxypentaerythritol 5 and hexaacrylate ("ARONIXM402" manufactured by Toagosei Co., Ltd.) Solvent: Cyclohexanone' [Photopolymerization initiator W, Y, Synthesis of T and V] The photopolymerization initiators W, Y, T and V described above were synthesized in the following manner. Synthesis of Photopolymerization Initiator W <Step 1> Synthesis of steroids in a nitrogen stream '12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, 53 mmoles N -Ethyl-3-nitro-oxazole is placed in an ice-cold reaction vessel. The reaction temperature was maintained at 5. (: In the following state, 64 mmol of 4-(2-methoxy-bumethyl-ethoxymethyl)-2-methyl-benzoguanidine chloride was slowly added dropwise to the mixture. After the completion of the dropwise addition The mixture was stirred at 2 (rc for 4 hours. Then, the reaction solution was poured into ice water to separate it into an oily phase and an aqueous phase. The liquid constituting the oily phase was dried using magnesium sulfate. Filtration removes the desiccant from the liquid, and further removes the solvent by evaporation-43-201042378. The above procedure is carried out to obtain a steroid. &lt;Step 2&gt; Synthesis of Photopolymerization Initiator W. In a nitrogen stream, 20 The above-mentioned carcass, 2.1 g (30 mmol) of hydroxylamine hydrochloride and 16.9 g of dimethylformamide were placed in a reaction vessel. The mixture was stirred at 8 (TC for 1 hour, cooled to room temperature). This was separated into an oily phase and an aqueous phase. The liquid constituting the oily phase was subjected to distillation to remove the solvent, and then, in the distillation residue, 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added. The mixture was stirred at 90 ° C for 1 hr, cooled to room temperature, and 5% NaOH was used. The aqueous solution is neutralized. Then, it is supplied to the oil-water separation, and the solvent is removed from the liquid constituting the oily phase by distillation, and further recrystallized using ethyl acetate as a solvent. The photopolymerization initiator W is obtained as described above. Synthesis of Photopolymerization Initiator Y &lt;Step 1&gt; Synthesis of Steroids In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, 53 mmoles N-(2-ethyl-hexyl)-3-nitro-oxazole was added to the ice-cold reaction vessel, and the reaction temperature was kept below 5 ° C, and the mixture was slowly dropped into the mixture. Milliol 4-(2-methoxy-l-methyl-ethoxy)-2-methyl-benzimid chloride. After the dropwise addition, the mixture was stirred at 20 ° C for 4 hours. 'Injecting the reaction liquid into ice water to separate it into an oily phase and an aqueous phase' will constitute a liquid of the oily phase, which is dried using magnesium sulfate. Then, the desiccant is removed from the liquid by filtration, and then by distillation. The solvent was removed, and the steroid was obtained as described above. &lt;Step 2&gt; Synthesis of Photopolymerization Initiator Y in a nitrogen stream 20 mol of the above carcass, 2.1 g (30 -44 - 201042378 mmol) of hydroxylamine hydrochloride and 16.9 g of dimethylformamide were placed in the reaction vessel. The mixture was stirred at 80 ° C. After 1 hour, it was cooled to room temperature to separate it into an oily phase and an aqueous phase. The liquid constituting the oily phase was removed by distillation, and then 25.4 g of butyl acetate and 2.45 g were added to the distillation residue. (24 mmol) acetic anhydride. The mixture was stirred at 90 ° C for 1 hour, cooled to room temperature, and neutralized using a 5% aqueous sodium hydroxide solution. Subsequently, it was supplied to oil-water separation, and the solvent was removed from the liquid constituting the oily phase by distillation, and further recrystallized using ethyl acetate as a solvent.进行 The photopolymerization initiator Y was obtained as described above. Synthesis of Photopolymerization Initiator T &lt;Step 1&gt; Synthesis of Steroids In a nitrogen stream '12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, 53 mmoles N -Ethyl-3-nitro-carbazole is placed in an ice-cold reaction vessel. While maintaining the reaction temperature at 5 ° C or lower, 64 mmol of 4-(ethoxymethyl)-2-methyl-benzoic acid chloride was slowly added dropwise to the mixed solution. After the completion of the dropwise addition, the mixture was stirred at 20 ° C for 4 hours. Subsequently, Q was poured into ice water to separate it into an oily phase and an aqueous phase, and a liquid constituting the oily phase was dried and dried using magnesium sulfate. Subsequently, the desiccant was removed from the liquid by filtration, and the solvent was removed by distillation. The above is carried out to obtain a corpus callosum. &lt;Step 2&gt; Synthesis of Photopolymerization Initiator T, 20 mol of the above-mentioned carcass, 2.1 g (30 mmol) of hydrochloric acid via a base amine, and 16.9 g of dimethylformamide in a nitrogen stream Put in the reaction vessel. The mixture was stirred at 80 ° C for 1 hour, and then cooled to room temperature to separate into an oily phase and an aqueous phase. The liquid constituting the oil phase was distilled off by -45 - 201042378, and then, in the distillation residue, 25.4 g of butyl acetate and 2.45 g (24 mmol) of acetic anhydride were added. The mixture was stirred at 90 ° C for 1 hour, cooled to room temperature, and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, it was supplied to oil-water separation, and the solvent was removed from the liquid constituting the oily phase by distillation, and further recrystallized using ethyl acetate as a solvent. The photopolymerization initiator T was obtained as described above. Synthesis of Photopolymerization Initiator V <Step 1> 醯 珣 Synthesis 〇 In a nitrogen stream, 12.60 g (95 mmol) of aluminum chloride, 126 g of 1,2-dichloroethane, 53 mmol The N-(2-ethyl-hexyl)-3-nitrocarbazole compound was placed in an ice-cold reaction vessel. While maintaining the reaction temperature below 5 ° C, 6 4 mmol of 4 · ( 2 -methoxy-1-methyl-ethoxy) 2 -methyl group was slowly added dropwise to the mixture. Benzoquinone chloride. After the completion of the dropwise addition, the mixture was stirred at 20 ° C for 4 hours. Subsequently, the reaction liquid was poured into ice water to separate it into an oily phase and an aqueous phase, and the liquid constituting the oily phase was dried and dried using magnesium sulfate. Subsequently, the desiccant was removed from the liquid by filtration, and Q was introduced to remove the solvent by distillation. The above was carried out to obtain a steroid. &lt;Step 2&gt; Synthesis of Photopolymerization Initiator V '20 mol of the above-mentioned carcass, 2.1 g (30 mmol) of hydroxylamine hydrochloride and 16 · 9 g of dimethylformamide in a nitrogen stream Put in the reaction vessel. The mixture was stirred at 80 ° C for 1 hour, and then cooled to room temperature to separate into an oily phase and an aqueous phase. The liquid constituting the oil phase was subjected to distillation to remove the solvent, and then, in the distillation residue, 25.4 g of butyl acetate and 3.12 g (24 mmol) of propionic anhydride were added. The mixture was stirred at 9 (rc for 1 hour, cooled to room temperature, and neutralized using a 5% aqueous sodium hydroxide solution. -46-201042378 Subsequently, the liquid was removed as described above (5): supplied to oil-water separation, and The photopolymerization initiator v is obtained by distillation from the agent constituting the oil phase and further recrystallized using ethyl acetate as a solvent. Ο By 6) Formula (7): 〇

I formula (8):

[Example 1] Each photosensitive coloring composition was evaluated in accordance with the method described in F to 25 and Comparative Examples 1 to 7. The results are shown in Table 3. -47- 201042378 (patterning of the calender sheet segment and the black matrix) Each photosensitive coloring composition was spin-coated on a glass substrate of 10 cm x 10 cm, and then pre-baked at 70 ° C for 15 minutes from the photosensitive coloring using a clean oven. The composition was freed of solvent. Thereby, a coating film having a thickness of about 2 /Z m was obtained. After the substrate was cooled to room temperature, the ultraviolet ray was exposed to the coating film by an illuminance of 25 mW/cm 2 through a photomask. The ultraviolet light source uses an ultra-high pressure mercury lamp. In the mask, a pattern area for evaluation of the linearity and development resistance and a pattern area for evaluation of the resolution are used. Here, the linearity and development resistance evaluation pattern region is a region in which a plurality of line patterns of a width of 100/zm are striped and formed as a light transmitting portion. Further, in the pattern area for the evaluation of the resolution, a region in which one line pattern of 2 5 μm width is stripe-shaped at a pitch of 5 〇 A m is used as a light transmitting portion. Subsequently, the exposed coating film 'is spray-imaged using a 23 ° C aqueous sodium carbonate solution, and washed with ion exchange - water and air-dried. Subsequently, it was post-baked for 30 minutes at 23 ° C using a clean oven. In this manner, a filter segment and a Q black matrix each containing a pattern region for resolution evaluation and a pattern region for evaluation of linearity and development resistance were obtained. Further, the minimum development time at which the unexposed portion is removed is set as the development time A, and twice the development time A is set as the development time B. When the development time A is developed, the minimum exposure amount at which the residual film ratio [= film thickness after post-baking + film thickness after drying before development] is 9% or more is set as the minimum exposure amount. (Resolution property evaluation) The line pattern for the evaluation of the resolution was observed by an optical microscope and the resolution was evaluated in accordance with the following three stages. Here, the poor resolution means that adjacent line patterns are connected, or a part of the line pattern is defective. -48- 201042378 〇: Good resolution △: Partial resolution defect X: Defective resolution (linearity evaluation) 'Linear and imaging tolerance evaluation was performed using an optical microscope and the following three lines were used. The stage evaluates linearity. 〇: good linearity △: partial linearity defect 0 X : linearity defect (developmental imaging evaluation) Regarding imaging tolerance, the residual film rate of the line pattern for evaluation of linearity and imaging tolerance was calculated, and the following four were Stage evaluation. Here, the residual film ratio 'refers to the ratio of the thickness of the coating film after post-baking to the thickness of the coating film after drying after image development at the development time A or B. ◦: Residual film rate is 90% or more △: Residual film rate is 70% or more 0 X : Residual film rate is 50% or more and less than 70% XX : Residual film rate is less than 50% (Appearance of coating surface wrinkles) The surface of the film was evaluated by a light microscope and the state of the surface of the coating film was evaluated in accordance with the following three stages using a line pattern for evaluation of linearity and developmental resistance. 〇: The surface of the coating film is good △: The surface of the coating film is slightly rough X: The surface of the coating film is wrinkled -49- 201042378 o o [ε€]

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v ~W d- ~5T 〇v 06 v 〇vvd, d, 〇vv J, ii V 酲0 0 Gull «i«8 ii HiiT dfis, 201042378 As shown in Table 3, the sensitization using Examples 1 to 25 The filter segments and the black matrix formed by the sexual coloring composition are somewhat different depending on the prescription, but either of them are inferior in practicality in resolution, linearity, imaging resistance, and wrinkle on the surface of the coating film. . In other words, a photosensitive coloring composition obtained by using a photopolymerization initiator (photopolymerization initiators W, Y, T, and V) represented by the formula (1) is used for image formation resistance and pattern linearity. good. In contrast, when another oxime ester-based photopolymerization initiator (photopolymerization initiator Z) is used, the development margin is small, and when the development time is twice, development resistance is poor, and a pattern of 0 pattern is generated. Poor sex and resolution. Further, as shown in Examples 1 to 25, particularly excellent development resistance can be achieved by appropriately setting the Ia/Μ ratio or the Ib/M ratio. Further, as shown in Examples 5 to 7, by using a photopolymerization initiator (photopolymerization initiators W, Y, T and V) represented by the formula (1) and an α-aminoalkyl group. The photopolymerization initiator can obtain a good filter segment without wrinkle on the surface of the coating film. "Test Example 2" 0 [Synthesis of Photopolymerization Initiator α] The photopolymerization initiator α represented by the following formula (9) was produced according to the method described in Japanese Patent No. 3,99,272. When the obtained compound was analyzed by 1H-NMR, the structure of the following formula (9) was confirmed. Equation (9):

-51-201042378 [Synthesis of Photopolymerization Initiator] The photopolymerization initiator represented by the following formula (10) was produced in accordance with the method described in Japanese Patent No. 3,992,725. When the obtained compound was analyzed by 1H-NMR, it was confirmed to be a structure of the following formula (10).

[Preparation of Red Pigment Dispersion] The following components were uniformly mixed by stirring using the following weight ratio. The acrylic resin solution was the same as that prepared in Test Example 1. Subsequently, the mixture was supplied to an Eiger mill ("MINIMODEL M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using a chrome oxide bead having a diameter of 1 mm and subjected to dispersion treatment for 2 hours. Further, filtration was carried out using a filter to remove coarse particles of 5 # m or more from the dispersion. Thereby, a red pigment dispersion P-R was obtained. Diketopyrrolopyrrole pigment (C.I. Pigment Red 254) 1 1.0 part ("IRGAPHOR RED B-CF" manufactured by CIBA JAPAN Co., Ltd.) The following diketopyrrolopyrrole pigment derivative 1.0 part -52- 201042378

Acrylic resin solution 4 0.0 parts cyclohexanone 4 8.0 parts [Modulation of green pigment dispersion]

The green pigment dispersion P-G was prepared in the same manner as in the method described in the red pigment dispersion P-R except that the pigment and the pigment derivative were each changed to the following pigments and pigment derivatives. Copper phthalocyanine pigment (CI Pigment Green 36) 7.1 parts ("LIONOL GREEN 6YK" manufactured by Toyo Ink Co., Ltd.) - azo pigment (C, I, Pigment Yellow 150) 3.9 parts (E4GN-GT, manufactured by LANXESS) "

The following azo pigment derivatives 1.0 part c2h5

[Preparation of Blue Pigment Dispersion] The green pigment dispersion P_B was prepared in the same manner as in the method described in the red pigment dispersion P-R except that the pigment and the pigment derivative were each changed to the following pigments and pigment derivatives. -53- 201042378 ε-type copper phthalocyanine pigment (C.I. Pigment Blue 15:6) ("HLIOGEN BLUE-L-6700F" manufactured by BASF) The following phthalocyanine pigment derivative

[Preparation of a black pigment dispersion] The black pigment dispersion P was prepared in the same manner as described in the red pigment dispersion p_r except that the pigment was changed to 12.0 parts of carbon black (Mitsubishi Chemical PJ "MA77"). -BK. [Preparation of photosensitive coloring composition] The materials of the photosensitive coloring composition were mixed at a ratio (weight ratio) shown in Table 4. After sufficiently stirring, the filter was filtered using a filter to remove coarse particles having a diameter of 1/zrn or more from the dispersion. Each of the photosensitive coloring compositions of Examples 26 to 36 and Comparative Examples 8 to 11 was prepared as described above. -54- 201042378 [Table 4 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Color Red Red Red Red Green Green Green Using Pigment Dispersion PR PR PR PR PR PG PG PG pigment dispersion 48.90 49.89 49.89 49.89 49.89 58.33 49.26 49.26 Acrylic resin solution 10.50 10.40 15.60 12.60 15.30 24.60 8.51 7.19 Photopolymerizable compound 3.90 1,50 2.00 5.00 2.00 2.00 1.50 2.00 Photopolymerization initiator α 0.20 0.30 0.30 0.20 0.20 0.22 0.30 Light Polymerization initiator /3 0.30 Photopolymerization bow 1 hair agent r sensitizer 0.20 Polyfunctional thiol 0.30 0.30 Organic solvent 36.50 37.91 31.91 32.31 32.61 14.85 40.23 40.95 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 1 Example 34 Example 35 Implementation Example 36 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Color Green Blue Black Red Green Blue Black - Using Pigment Dispersion PG PB P-BK PR PG PB P-BK Pigment Dispersion 49.26 27.95 75.00 49.89 49.26 27.95 75.00 Acrylic Resin Solution 7.19 18.81 8.50 15.60 7.19 17.01 9.00 Photopolymerizable compound 2.25 3.00 3.20 2.00 2.25 3.50 2.20 Photopolymerization initiator α 0.60 0.80 Photopolymerization initiator 泠0.22 Photopolymerization initiator r 0.20 0.22 0.40 1.00 Sensitizer 0.20 Polyfunctional thiol organic solvent 41.08 49.64 12.50 32.31 41.08 50.94 12.80 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 Ο In Table 4, the general name is as follows, specifically as follows. Photopolymerizable compound:

("ARONIXM402" manufactured by Toagosei Co., Ltd.) 1,2-octanedione-1-[4-(phenylthio)phenyl-, 2-(0-benzamide)] (IRGACURE ΟΧΕ01, manufactured by CIBA JAPAN) ") Sensitizer: 4,4'-bis(diethylamino)diphenyl ketone ("EAB-F" manufactured by HODOGAYA Co., Ltd.) Polyfunctional thiol: Trimethylolpropane thiopropionate organic solvent: -55- 201042378 Cyclohexanone [pattern formation of the filter segment and the black matrix] The coating film of each of the photosensitive coloring compositions of Examples 26 to 36 and Comparative Examples 8 to 1 was post-baked The manner of the thickness shown in Table 5 was spin-coated on a glass substrate of 10 cm x 10 cm. Subsequently, the solvent was removed from the photosensitive coloring composition using a clean oven and prebaking at 70 ° C for 15 minutes. After the substrate was cooled to room temperature, the coating film was exposed to ultraviolet rays through a photomask. Subsequently, the exposed coating film was spray-imaged using a 23 ° C aqueous sodium carbonate solution, washed with ion-exchanged water, and air-dried. Subsequently, post-baking was carried out at 23 ° C for 30 minutes using a clean oven. In this manner, a stripe-shaped filter segment or a black matrix is formed on the substrate. [Evaluation] The photosensitivity coloring compositions of Examples 26 to 36 and Comparative Examples 8 to 1 were evaluated according to the following methods. The results are shown in Table 5. (Sensitivity Evaluation) Here, the minimum exposure amount of the size of the calender sheet section or the black matrix and the size of the transmissive portion of the photomask is set as the sensitivity of the photosensitive coloring composition. The smaller the exposure, the higher the sensitivity. The rating of the evaluation is as follows. 〇: less than 50 mJ/cm 2 Δ : 50 mJ/cm 2 or more, less than l 〇〇 mJ/cm 2 X: 100 mJ/cm 2 or more (pattern shape evaluation) The pattern shape of the filter segment and the black matrix is linear and Evaluation of the viewpoint of the shape of the section. The linearity of the pattern was evaluated by observation using an optical microscope. -56- 201042378 Rating is as follows. 〇: good linearity △: partial linearity defect X: linearity defect The cross-sectional shape of the pattern was evaluated by observation using a scanning electron microscope (SEM). When the cross-sectional shape of the pattern is a tapered shape, pattern defects are less likely to occur.时 When the cross-sectional shape of the pattern is a reverse cone shape, pattern defects are likely to occur. The rating of the evaluation is as follows. 〇: Striated cone △: Non-conical shape 'X: Reverse cone shape (Evaluation of imaging tolerance) The imaging tolerance was evaluated based on the residual film ratio. Here, the residual film ratio is a ratio of the thickness of the coating film after post-baking to the thickness of the coating film after drying after development when the amount of exposure is set to 100 μm/cm 2 . The greater the residual film rate, the better the imaging tolerance. The rating of the evaluation is as follows. ◎ : 80% or more 〇: 7 5 % or more, less than 80 % △ : 70 % or more, less than 7 5 % X : less than 70% -57- 201042378 [Table 5]

1 Example 34 Example 35 Example 36 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Color Green Blue Black Red Green Blue Black Film Thickness (μιη) 1.70 1.80 1.10 1.40 1.70 1.80 1.10 Pigment Rhyme (ms%) 43% 26% 43% 39% 43% 26% 45% M/P 0.42 0.50 0.42 0.28 0,42 0.62 0.28 IM 0.10 0.20 0.25 0.10 0.10 0.11 0.45 IM - • - - - 0.17 • Sensitivity Δ 〇〇XXXX Pattern linearity Δ 〇〇〇 △ XX pattern sectional shape 〇〇〇 XX Δ X residual film rate ◎ ◎ 〇〇〇 XX Example 26 寅 Example 27 Example 28 Window Example 29 Example 30 Example 31 Example 32 Example 33 Color Red, red, red, green, green, and green film thickness (4) 1.40 1.40 1.40 1.40 1.40 1.70 1.70 1.70 Pigment content (% by weight) 37% 43% 39% 34% 39% 37% 44% 43% W? 1M 0.65 0.25 0.28 0.77 0.27 0.21 0 *27 0.42 0.05 0.20 0.10 0.04 0.10 0.11 0.20 0.15 Ib/M • • - - - 0.33 • Sensitivity Δ 〇〇 △ Δ 〇〇〇 Pattern linearity Δ Δ 〇 Δ 〇 Δ 〇 〇 Pattern section shape △ 〇〇 △ 〇 Δ 〇〇mm 〇〇◎ 〇〇◎ ◎ ◎

The meaning of the item name in Table 5 is as follows. Film thickness: Film thickness of the filter segment or black matrix Pigment content: Pigment ratio M/P = (weight of photopolymerizable compound (C)) / (based on the total solid content of the photosensitive coloring composition) / ( Transparent resin (B) weight)

Ia/M = (total weight of photopolymerization initiator) / (weight of photopolymerizable compound (C))

Ib/M = (the sum of the total weight of the photopolymerization initiator and the weight of the sensitizer (E)) / (the weight of the photopolymerizable compound (C)) As shown in Table 5, the formula (2) or (3) is used. The photosensitive coloring composition of the photopolymerization initiator (D) shown is highly sensitive, and the obtained pattern has good linearity and cross-sectional shape. In contrast, in Comparative Examples 8 to 1 1 -58-201042378, the photosensitive coloring composition obtained by using another photopolymerization initiator r is a sensitivity, a linearity of a pattern, and a cross-sectional shape. The system is poor, and it is impossible to get all of them. Further, as shown in the embodiments 26 to 36, the sensitivity and the linearity of the pattern and the characteristic of the cross-sectional shape can be achieved by appropriately setting the Μ/P ratio or the Ι/M ratio'. [Simple description of the diagram] None. 0 [Main component symbol description] None. 〇

Claims (1)

201042378 VII. Patent application scope: 1. A photosensitive coloring composition containing a pigment (A), a transparent resin (B), a photopolymerizable compound (C) and selected from the following formulas (1) to (3) At least one photopolymerization initiator (D) of the group consisting of the compounds shown, 'Formula (1): 〇 [In formula (1), X1, X3 and X6 each independently represent R&quot;, 0R11, COR11, SR11, CONR12R13 or CN, and X2 represents a hospital base having 1 to 20 carbon atoms which may also have a substituent An aryl group having 6 to 30 carbon atoms which may have a substituent, an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or a carbon atom having 2 to a ring group which may have a substituent, X4 and X5 each independently represents R11, OR11, SR11, D w C Ο R 11 , C Ο NR 1 2 R13, N R1 2 C Ο R11, Ο C Ο R1 1 , c 〇〇 R11, SCOR11, COSR11, COSR11, CSOR11, CN, a halogen atom or a hydroxyl group, and R11, R12 and R13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and may have a carbon number of {go group An aryl group of 6 to 30, an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 20 carbon atoms which may have a substituent, and a and b each independently represent 〇 to 3 Integer] -60- 201042378 (2) [In the formula (2) and the formula (3), X1 to X4 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms]. The photosensitive coloring composition of the first aspect of the invention, wherein the photopolymerization initiator (D) is represented by the formula (1). 3. The photosensitive coloring composition of claim 2, wherein the ratio of the weight U of the photopolymerization initiator (D) to the weight of the photopolymerizable compound (C) is Ia/M is 0.05 to Within the range of 0.50. 4. The photosensitive coloring composition of the second or third aspect of the patent application, wherein the sensitizer (E) is further contained, and the total weight Ib of the photopolymerization initiator (D) and the sensitizer (E) is The weight ratio of the photopolymerizable compound (C) to Ib/M is in the range of 〇.10 to 〇.6〇. 5. The photosensitive coloring composition of the first aspect of the invention, wherein the photopolymerization initiator (D) is represented by the formula (2) or (3). 201042378 6. The photosensitive coloring composition of claim 5, wherein the ratio of the weight P of the transparent resin (B) to the weight 前述/P of the photopolymerizable compound (C) is 0.10 to 0.60. In the range. 7. The photosensitive coloring composition of claim 5 or 6 wherein * the ratio of the weight U of the photopolymerization initiator (D) to the weight of the photopolymerization initiator (C) is Ia/M 〇·〇5 to 0.25 range. The photosensitive coloring composition according to any one of claims 1 to 7, which further contains an α-aminoalkylethene-based photopolymerization initiator. The photosensitive coloring composition according to any one of claims 1 to 8, which further contains a polyfunctional thiol (F). A color filter comprising at least one of a filter segment and a black matrix formed by the photosensitive coloring composition according to any one of claims 1 to 9. -62- 201042378 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: te 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: