JP2018101073A - Photosensitive coloring composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition for a color filter which is excellent in cross-sectional shape and coating film resistance while imparting good developability even when a content of a coloring agent is high, and a color filter using the same.SOLUTION: The photosensitive coloring composition for a color filter is provided which contains a colorant (A), a resin type dispersant (B), a photopolymerizable monomer (C), a photopolymerization initiator (D) and an organic solvent (E), and in which a content of the colorant (A) is 40 wt.% or more in 100 wt.% of the total solid content of the photosensitive coloring composition for a color filter, and the photosensitive coloring composition contains a specific photopolymerizable monomer (C).SELECTED DRAWING: None

Description

  The present invention is a color filter coloring composition used for manufacturing a color filter used in a color liquid crystal display device, a color imaging device, a quantum dot display device, an organic EL display device, and the like, and formed using the same. The present invention relates to a color filter having a filter segment.

  As an image display device using a color filter, for example, (A) a backlight as a light source, a liquid crystal as an optical shutter, and a combination of color filters having color adjustment functions (color conversion function, color separation function, color correction function, etc.) And (B) a synthetic white organic EL light source, and an organic EL display device comprising a combination of color filters having a color adjustment function (color conversion function, color separation function, color correction function, etc.).

  In the color liquid crystal display device of (A), a liquid crystal layer sandwiched between two polarizing plates controls the degree of polarization of light that has passed through the first polarizing plate and passes through the second polarizing plate. This is a display device that performs display by controlling the amount of light, and the type using twisted nematic (TN) type liquid crystal is the mainstream. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  In general, a color filter is formed in a fine strip (stripe) shape formed of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) formed on the surface of a transparent substrate such as glass. The filter segments (pixels) are arranged in parallel or intersecting with each other, or the fine filter segments are arranged in a constant vertical and horizontal arrangement. The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue. Recently, in addition to a red filter layer (R), a green filter layer (G), and a blue filter layer (B), a filter segment including a yellow filter layer (Y) has been used.

  A transparent electrode for driving a liquid crystal is generally formed on the color filter used in the color liquid crystal display device by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Is formed. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  As the synthetic white light source of the organic EL display device of (B), there are a light source having a two-wavelength peak, a light source having a three-wavelength peak, and a light source having a number of peaks in the visible light region. Synthetic white light is obtained by mixing or layering.

  Since the organic EL display device can directly turn on / off the light source of the pixel by a TFT (thin film transistor) or the like, it is possible to perform black display by turning off the light emission of the designated pixel. Therefore, a deflecting plate used in the liquid crystal display device is not required in the light emitting device, and it is not necessary to control the liquid crystal body. For this reason, the amount of transmitted light in the display device increases, and energy consumption can be greatly reduced by turning off the light emitting device in black display. In addition, it is possible to reproduce true dark black, and the contrast ratio can be increased. As an organic EL color display device in which the problems in the liquid crystal display device are solved, for example, a product such as “XEL-1” manufactured by SONY is already on the market. (For example, see Patent Document 1)

  The organic EL display device is different from the liquid crystal color display device in that it has excellent display performance such as a high contrast ratio, a wide viewing angle, a fast response speed, and a wide color reproducibility. In particular, in order to obtain a high color gamut, it is necessary to increase the color purity of each color filter segment in the color filter.

  In recent years, color display devices have formed a large market for televisions, car navigation systems, personal computers, and portable terminals. There is an increasing demand for high color reproducibility and high brightness in a color filter in which filter segments for each color are arranged.

  In order to improve the color reproduction characteristics of the color filter, it is necessary to increase the content of the colorant in the photosensitive coloring composition or to increase the film thickness. In the method of increasing the content of the colorant, problems such as deterioration in developability, deterioration in pattern shape, and deterioration in coating film resistance occur due to a decrease in the resin and photopolymerizable compound that are curable materials. Also. In the method of increasing the film thickness, exposure light does not reach the bottom of the film, and problems such as a defective pattern shape tend to occur. Furthermore, since there is an increasing demand for thinner color display devices and there is a tendency to reduce the film thickness, a photosensitive coloring composition containing a colorant at a high concentration has improved developability and shape. There is a need for improvement and improved coating film resistance.

  In order to improve the coating film resistance, it is necessary to increase the sensitivity of the photosensitive coloring composition. In general, (1) imparting a reactive double bond to the binder resin, and (2) a photopolymerizable monomer. The body is selected or increased, and (3) a highly sensitive photopolymerization initiator is selected or increased.

  However, there is a limit to the improvement in sensitivity only by providing a double bond to the binder resin, and when the amount of the photopolymerizable monomer is increased, problems such as tackiness occur. On the other hand, in increasing the amount of photopolymerization initiator, the effect of improving the sensitivity is great, but there is a problem that the brightness is lowered by coloring in the heat treatment step depending on the type of photopolymerization initiator.

Japanese Patent Laid-Open No. 2005-10091

  Therefore, in the present invention, even when a colorant is contained at a high concentration, a photosensitive coloring composition having good developability and pattern shape and sufficient coating film resistance, formed using the photosensitive coloring composition It is an object to provide an improved color filter.

  As a result of intensive research to solve the above problems, the present inventors have found that the content of the colorant is 40% by weight or more based on the total solid content of the photosensitive coloring composition for color filters. However, by using a specific photopolymerizable monomer (C), it has been found that developability and pattern shape are good and coating film resistance can be sufficiently provided. The present invention has been made based on the above.

That is, the present invention contains a colorant (A), a resin-type dispersant (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and an organic solvent (E). A photosensitive coloring composition for a color filter, wherein the content of the colorant (A) is 40% by weight or more based on the total solid content of the photosensitive coloring composition for a color filter, and the light The photosensitive coloring composition for color filters, wherein the polymerizable monomer (C) contains at least one photopolymerizable monomer (C1) selected from the following general formulas (1) and (2) Related to things.
(Formula _{1) :( CH 2 = C (} -R) -C (= O) -O-CH 2) 3 -CCH 2 CH 3
(Formula _{2) :( CH 2 = C (} -R) -C (= O) - (O-R 1) n-O-CH 2) 3 -CCH 2 CH 3
[Wherein, R represents H or CH ₃ , R ₁ represents C ₂ H ₄ or C ₃ H ₆ , and n = 1 or 2. ]

The present invention also relates to the photosensitive coloring composition for a color filter, wherein the resin-type dispersant (B) has a glass transition temperature (Tg) of 20 to 100 ° C.

The present invention also relates to the above photosensitive coloring composition for color filters, wherein the photopolymerizable monomer (C) further contains a polyfunctional urethane acrylate (C2).

The present invention also relates to the photosensitive coloring composition for a color filter, wherein the photopolymerization initiator (D) contains an oxime ester compound (D1).

The present invention also relates to the photosensitive coloring composition for a color filter, wherein the photopolymerization initiator (D) contains an acetophenone compound (D2).

The present invention further relates to the photosensitive coloring composition for a color filter, further comprising a sensitizer (F), wherein the sensitizer (F) contains a thioxanthone compound (F1).

The present invention further relates to the photosensitive coloring composition for a color filter, further comprising an antioxidant (G).

The present invention also relates to a color filter comprising a filter segment formed on the base material from the photosensitive coloring composition for a color filter.

  With the photosensitive coloring composition for color filters of the present invention, even when a colorant is contained at a high concentration, by using a specific photopolymerizable monomer (C), developability and pattern shape are good, A color filter having sufficient coating resistance can be formed.

Hereinafter, the present invention will be described in detail.
In the present application, when expressed as “(meth) acrylate”, “(meth) acrylic acid”, or “(meth) acrylamide”, unless otherwise specified, “acrylate and / or methacrylate”, It shall represent “acrylic acid and / or methacrylic acid” or “acrylamide and / or methacrylamide”.
Further, “CI” mentioned below means a color index (CI).

<Colorant (A)>
As the colorant (A) contained in the photosensitive coloring composition of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance are preferable, and organic pigments are usually used. Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition for color filters of this invention is shown by a color index number.
Moreover, as a coloring agent (A), dye can be contained in the range which does not reduce heat resistance.

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Among these, azo pigments, diketopyrrolopyrrole-based, anthraquinone-based, quinophthalone-based, isoindoline-based, perinone-based, perylene-based, and benzimidazolone-based pigments are exemplified from the viewpoint of brightness and coloring power. Specifically, C.I. I. Pigment Red 176, 177, 179, 242, 254, and 269 are preferable.

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

  Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 Can be mentioned. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Green 7, 36, 58, 59, 62, and 63. Moreover, the zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like can also be used, and the invention is not particularly limited thereto.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, 231 and the like. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment yellow 138, 139, 150, 185, 231.

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

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

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

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

The photosensitive coloring composition for color filters of this invention contains the coloring agent (A), and can form the filter segment of each color which comprises a color filter.
The content of the colorant is preferably in the range of 40% by weight or more, more preferably in the range of 45% by weight or more based on the weight of the total solid content of the photosensitive coloring composition for color filter. When the content is less than 40% by weight, when a color filter with high color reproducibility is produced, the film thickness becomes thicker than the general film thickness range (about 1.0 to 3.0 μm). Therefore, it is not preferable. When the content is less than 40% by weight, at least one photopolymerizable monomer (C1) selected from the following general formulas (1) and (2) is used as the photopolymerizable monomer (C). If it is contained, it is not preferable because the pattern is likely to be chipped in the development step as compared with the case where the content of the colorant in the coating film is large.

(Formula _{1) :( CH 2 = C (} -R) -C (= O) -O-CH 2) 3 -CCH 2 CH 3
(Formula _{2) :( CH 2 = C (} -R) -C (= O) - (O-R 1) n-O-CH 2) 3 -CCH 2 CH 3
[Wherein, R represents H or CH ₃ , R ₁ represents C ₂ H ₄ or C ₃ H ₆ , and n = 1 or 2. ]

(Miniaturization of pigment)
When the colorant used in the coloring composition of the present invention is a pigment, it can be refined by a salt milling process or the like. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. When the thickness is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Resin type dispersant (B)>
The resin-type dispersant (B) has a coloring agent, a coloring agent affinity portion having a property of adsorbing to a pigment derivative added to improve dispersibility, and a portion compatible with the coloring agent carrier. Adsorbed to the added colorant and functions to stabilize dispersion in the colorant carrier. The colorant carrier refers to a component excluding a colorant such as a binder resin and a photopolymerizable monomer. The resin-type dispersant of the present invention may have either an acidic substituent or a basic substituent as an affinity site for the colorant.

The basic structure of the resin-type dispersant is not particularly limited, and examples thereof include general resins such as acrylic resins, polyester resins, polyether resins, urethane resins, silicone resins, epoxy resins, and vinyl acetate resins.

  Examples of the acidic substituent include a phosphoric acid group, a sulfonic acid group, and a carboxyl group. Further, trimellitic acid and / or pyromellitic acid partially esterified are preferably used. In some cases, an aromatic ring having two or more acidic substituents may be a unit having one acidic substituent by a plurality of direct bonds and / or linking groups. Especially, it is preferable to have two or more carboxyl groups in one molecule. A dispersant having two or more carboxyl groups in one molecule has more adsorbing groups to the colorant than a resin-type dispersant having zero or one carboxyl group in one molecule. This is preferable because it has a strong function of stabilizing the dispersion on the carrier, the polarity of the dispersant is increased, and higher dispersion stability can be secured.

Examples of the resin-type dispersant having a basic group include a nitrogen atom-containing graft copolymer, and a nitrogen atom-containing acrylic having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, or the like in the side chain. A block copolymer and a urethane polymer dispersant are preferred.

  As the resin-type dispersant, those having an acidic substituent, an aromatic group or the like in the main chain or terminal of the linear resin, or in the main chain or side chain of the comb-like resin, in a block or randomly are preferable. Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, poly ( An amide formed by a reaction between a lower alkyleneimine) and a polyester having a free carboxyl group, a salt thereof, or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble High molecular compounds, polyesters, modified poly (meth) acrylates, ethylene oxide / propylene oxide adducts, phosphate esters, and the like are used. These may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  As a site | part with high affinity to a dispersion medium of the resin type dispersing agent of this invention, the at least 1 sort (s) of polymer unit chosen from polyester, polyether, and poly (meth) acrylate is preferable.

  For example, as polyester, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, One or more alcohols such as glycerin or hexanetriol, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid ,Guru Conic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexa And polyester polyols obtained by cocondensation with one or more carboxylic acids such as tricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid.

  For example, as the polyether, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane Diol, 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol , Alcohols such as glycerin or hexanetriol, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether Others include modified polyether polyols and the like obtained by ring-opening polymerization of various (cyclic) ether bond-containing compounds such as allyl glycidyl ether.

  For example, as poly (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, oxetane (meth) acrylate, etc. Alkoxypolyalkylene glycol (meth) acrylates such as xypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate, (meth) acrylamide, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta) ) N-substituted (meth) acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( Examples include homopolymers and copolymers such as amino group-containing (meth) acrylates such as (meth) acrylate and nitriles such as (meth) acrylonitrile. These may be used alone or in combination, or may be in the form of a block polymer, graft polymer or random polymer.

  Examples of commercially available resin-type pigment dispersants having acidic groups include Solsperse 3000, Solsperse 21000, Solsperse 26000, Solsperse 36600, Solsperse 41000, Solsperse 44000, Solsperse 46000, Solsperse 55000 (manufactured by Avicia); 108, Dispersic 110, Dispersic 111, Dispersic 112, Dispersic 116, Dispersic 142, Dispersic 180, Dispersic 2001, (manufactured by BYK Chemie); Disparon 3600N, Disparon 1850 (manufactured by Enomoto Kasei); Ajinomoto Fine Techno Co.); EFKA4401, EFKA4550 (Fuka Additives Co., Ltd.), etc. That, without being limited thereto.

As a commercially available resin type dispersant having a basic group, Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, manufactured by Big Chemie Japan, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, SOLPERSE-3000, 9000, 13000, 13240, 13650 made by Lubrizol Japan, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen et al. 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, manufactured by BASF Japan , 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066 5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB411, PB821, PB822, PB824, and the like.

  Among these, it is preferable that the photosensitive coloring composition for color filters in the present invention contains the resin-type dispersant (B) having a glass transition temperature (Tg) of 20 to 100 ° C. . Thereby, the developability is excellent and the coating film resistance is excellent. When Tg is lower than 20 ° C., chipping of the pattern occurs or chemical resistance of the coating film deteriorates. When Tg is higher than 100 ° C., developability is remarkably deteriorated. In particular, when it is in the range of 35 to 95 ° C., the balance between the developability of the coating film and the chemical resistance is more preferable.

In addition, the glass transition temperature in this invention has shown the value computed by the following Fox formula from Tg of each homopolymer to copolymerize.
Fox formula 1 / Tg = W1 / Tg1 + W2 / Tg2 +... + Wn / Tgn
W1 to Wn represent the weight fraction of the monomer used, and Tg1 to Tgn represent the glass transition temperature of the monomer homopolymer (unit is absolute temperature “K”).
Regarding the Tg of the main homopolymer used for the calculation, the numerical values described in the polymer handbook can be used. The numerical values are exemplified below.
ε-caprolactone: -60 ° C (213K)
Ethyl acrylate: -22 ° C (251K)
t-butyl acrylate: 41 ° C. (314 K)
Methacrylic acid: 130 ° C (403K)
Methyl methacrylate: 105 ° C (378K)
n-butyl acrylate: -54 ° C (219K)
2-methoxyethyl acrylate: -50 ° C (223K)
Diethylaminoethyl methacrylate: 18 ° C (291K)
1-adamantyl methacrylate: 250 ° C. (523 K)

<Other dispersants>
When dispersing the colorant in the colorant carrier, other dispersants other than the resin-type dispersant (B) such as a pigment derivative and a surfactant may be appropriately contained. Since these dispersants have a great effect of preventing re-aggregation of the colorant after dispersion, a color composition obtained by dispersing the colorant in the colorant carrier has good spectral characteristics and viscosity stability.

(Dye derivative)
Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount of the pigment derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, most preferably 3 with respect to 100 parts by mass of the colorant (A) from the viewpoint of improving the dispersibility of the additive colorant. More than part by mass. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, and more preferably 35 parts by mass or less with respect to 100 parts by mass of the colorant (A).

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The compounding amount of the surfactant is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant (A). When the blending amount of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the added effect, and when it is more than 55 parts by mass, the dispersion may be adversely affected by an excessive dispersant.

<Binder resin>
The photosensitive coloring composition for a color filter of the present invention may contain a binder resin as a colorant-dispersed or dyed / penetrated material. Examples of the binder resin include a thermoplastic resin and a thermosetting resin. The resin is preferably a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type photosensitive coloring composition, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic substituent containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or an isobutylene / (anhydrous) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because of its high heat resistance and transparency. It is done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Or 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. It may be used in combination. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

  In order to disperse the colorant preferably, the weight average molecular weight (Mw) of the resin is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  In addition, from the viewpoint of dispersibility, stability, developability, and heat resistance of the colorant, a carboxyl group that functions as a colorant adsorption group and an alkali-soluble group during development, an aliphatic group that functions as an affinity group for the colorant carrier and the solvent. The balance between the group and the aromatic group is important for the dispersibility of the pigment, the permeability of the developer in the coating film, the solubility of the developer in the uncured part, and the durability, and a resin having an acid value of 20 to 300 mgKOH / g. It is preferable to use it. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The resin is preferably used in an amount of 20 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 200 parts by weight or less. More preferably, it is 30-150 weight part. The chromaticity region can be expanded by such a composition ratio of the pigment.

<Photopolymerizable monomer (C)>
The photosensitive coloring composition of the present invention contains (C1) as a photopolymerizable monomer. In general, the photosensitive coloring composition deteriorates the developability of the coating film when the content of the colorant is increased. However, by containing the photopolymerizable monomer (C1), a good developability can be obtained. The productivity of the filter is improved. This is because the photopolymerizable monomer (C1) has three unsaturated bonding groups in the molecule, although the molecular weight is in the range of 250 to 650, which is a relatively low molecular weight. It is characterized by a high number of bonding groups. Thereby, even when the content of the colorant is high, both good developability and high exposure sensitivity can be achieved. On the other hand, when looking at the cross-linked structure formed by the photopolymerizable monomer (C1), compared with the photopolymerizable monomer having more unsaturated bond groups in the molecule and a large molecular weight. A crosslinked structure with little entanglement. Therefore, problems such as chipping of the pattern at the time of development occur, but when the content of the colorant is high, the development resistance of the colorant itself is high. Can be used.
(Photopolymerizable monomer (C1))
The photosensitive coloring composition for color filters of the present invention contains at least one photopolymerizable monomer (C1) selected from the following formulas (1) and (2).
(Formula _{1) :( CH 2 = C (} -R) -C (= O) -O-CH 2) 3 -CCH 2 CH 3
(Formula _{2) :( CH 2 = C (} -R) -C (= O) - (O-R 1) n-O-CH 2) 3 -CCH 2 CH 3
[Wherein, R represents H or CH ₃ , R ₁ represents C ₂ H ₄ or C ₃ H ₆ , and n = 1 or 2. ]

As a commercially available monomer represented by the general formula (1), Aronix M-309 manufactured by Toa Gosei Co., Ltd., SR351S manufactured by Sakai Kogyo Co., Ltd., A-TMPT manufactured by Shin-Nakamura Chemical Co., Ltd., Biscoat # manufactured by Osaka Organic Chemical Co., Ltd. 295, SR350 manufactured by Sakai Kogyo Co., Ltd., Sanester TMP manufactured by Sanshin Chemical Industry Co., Ltd. and the like.

As a commercially available monomer represented by the general formula (2), Aronix M-310, Aronix M-321, Aronix M-350, Aronix M-360, manufactured by Toa Gosei Co., Ltd. SR454 manufactured by KK, Viscoat # 360 manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like.

These photopolymerizable monomers (C1) can be used singly or as a mixture of two or more at any ratio as required.

(Photopolymerizable monomer (C2))
The photosensitive coloring composition for color filters of this invention can contain polyfunctional urethane acrylate (C2). When the colorant content of the photosensitive coloring composition is high, the chemical resistance of the coating film may be deteriorated because the amount of the coating film crosslinking component is reduced. High tolerance can be imparted.

There is no limitation on the structure of the polyfunctional urethane acrylate (C2), and the polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, or a polyfunctional isocyanate is reacted with an alcohol and further having a hydroxyl group. The polyfunctional urethane acrylate etc. which are obtained by making (meth) acrylate react are mentioned.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (meth) acrylate, dipentaerythritol caprolactone modified penta (meth) acrylate, glycerol acrylate Methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, containing epoxy groups The reaction product of compound and the carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

Moreover, although there is no restriction | limiting in the structure of alcohol, when a polyhydric alcohol is used, since the crosslinking degree of a cured coating film becomes high and coating-film resistance goes up, it is preferable. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

The photopolymerizable monomer (C2) that can be used in the colored composition of the present invention includes, in addition to the above-described polyfunctional urethane acrylate, a (meth) acrylate having a hydroxyl group, a polyfunctional isocyanate, and alcohol. When the polyfunctional isocyanate is reacted with, and the (meth) acrylate having a hydroxyl group is further reacted, a component having a double bond group not obtained as a polyfunctional urethane acrylate may be contained as another monomer.

  A commercially available polyfunctional acrylate can also be used for the photomonomer (C2) of the present invention. Specifically, KAYARAD UX-3204, KAYARAD UX-4101, KAYARAD UX-6100, KAYARAD UX-6101, KAYARAD UX-7101, KAYARAD UX-8101, KAYARAD UX-0937, X KAYARAD DPHA-40H, KAYARAD UX-5005, and Aronix M-1100, Aronix M-1200 manufactured by Toa Gosei Co., Ltd. UA-7100, UA-W2A, KSM-4I, KUA-6I, KUA-9N, KUA-10H, etc. manufactured by KSM Co., Ltd. can be preferably used.

(Other photopolymerizable monomers)
In the present invention, in addition to the photopolymerizable monomer (C1) and the photopolymerizable monomer (C2), other photopolymerizable monomers may be included. Examples of other photopolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β -Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, Opentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylic Various acrylic esters and methacrylic esters such as acid esters and epoxy (meth) acrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N -Hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, etc. are mentioned, but are not necessarily limited to these. There is no.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 100 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator (D)>
In the colored composition of the present invention, the composition is cured by ultraviolet irradiation and a photopolymerization initiator (D) is added to form a filter segment by a photolithography method, and a solvent development type or alkali development type photosensitivity is added. It can be prepared in the form of a colored composition.

(Oxime ester compound (D1))
The photosensitive coloring composition for color filters of this invention can contain an oxime ester type compound (D1) as a photoinitiator.
When the oxime ester compound (D1) absorbs ultraviolet rays, the N—O bond of the oxime is cleaved to generate an iminyl radical and an alkyloxy radical. Since these radicals are further decomposed to generate radicals with high activity, a pattern can be formed with a small exposure amount. When the concentration of the colorant in the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the curing degree of the coating film may be low. The More preferably, when it has a carbazole group, it can be set as the composition excellent in the brightness and color purity. Particularly preferred is an oxime ester photopolymerization initiator represented by the general formula (3).

(Oxime ester photopolymerization initiator represented by the general formula (3))
General formula (3)

In general formula (3),
Y ¹ is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group,
Y ² is a hydrogen atom or an optionally substituted alkenyl group, alkyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group , An alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group.
Z is a direct bond or a -CO- group,
Y ³ is a monovalent organic group including a carbazole group which may have a substituent, a Ph-S-Ph- group (Ph represents a phenyl group or a phenylene group which may have a substituent). Etc.

Examples of the alkenyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkenyl group having 1 to 18 carbon atoms, and these include a plurality of carbon atoms in the structure. -It may have a carbon double bond, and specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group. 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1 , 3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like, but are not limited thereto.

The alkyl group which may have a substituent for Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and optionally 1 Examples include a linear, branched, monocyclic or condensed polycyclic alkyl group interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include —CH ₂ —O—CH ₃ , —CH _2. —CH ₂ —O—CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1) To 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —. _{CH 3 -, - CH 2 -CH-} (OCH 3) but ₂ and the like, but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following, but are not limited thereto. Is not to be done.

The alkyloxy group which may have a substituent for Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Examples include linear, branched, monocyclic or condensed polycyclic alkyloxy groups optionally interrupted by one or more —O—. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boroni Group, 4-decyl cyclohexyl although group and the like, but is not limited thereto. Specific examples of the linear or branched alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , _{-O-CH 2 -CH 2 -O-} CH 2 -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n -CH ₃ (wherein n is 1 to _{8), - O- (CH 2} -CH 2 -CH 2 -O) m -CH 3 ( here m is 5 1), - O-CH _{2 -CH (CH 3) -O-} CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more of —O— include the following. It is not limited.

Examples of the aryl group that may have a substituent in Y ¹ include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group, and 2-naphthyl. Group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group Group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p -Cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromopheny Group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group, etc., but are not limited thereto. It is not something.

Examples of the aryloxy group which may have a substituent for Y ¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples include a phenoxy group, a 1-naphthyloxy group, 2- Naphtyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group , 9-fluorenyloxy group and the like, but are not limited thereto.

Examples of the heterocyclic group that may have a substituent for Y ¹ include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl Group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquino Lyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, Imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl of the group and the like, but is not limited thereto.

Examples of the heterocyclic oxy group that may have a substituent for Y ¹ include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyl. Examples thereof include, but are not limited to, a ruoxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group.

Examples of the alkylsulfanyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples include a methylthio group. , Ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like, but are not limited thereto.

Examples of the arylsulfanyl group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group, 2- Examples thereof include, but are not limited to, a naphthylthio group, a 9-anthrylthio group, and a 9-phenanthrylthio group.

The alkylsulfinyl group which may have a substituent in Y ¹ is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, Butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, etc. Although it is mentioned, it is not limited to these.

The arylsulfinyl group which may have a substituent in Y ¹ is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specific examples thereof include a phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4- Examples thereof include, but are not limited to, a phenylsulfanylphenylsulfinyl group and a 4-dimethylaminophenylsulfinyl group.

The alkylsulfonyl group which may have a substituent in Y ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, Butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group, etc. Although it is mentioned, it is not limited to these.

The arylsulfonyl group which may have a substituent for Y ¹ is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfo Examples thereof include, but are not limited to, a nyl group and a 4-dimethylaminophenylsulfonyl group.

Examples of the acyl group which may have a substituent for Y ¹ include a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, A carbonyl group substituted by an alkyloxy group having 2 to 20 carbon atoms, a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, or a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms. Examples include a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms including a substituted carbonyl group, a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom is bonded. Specific examples include formyl Group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl Group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyl Oxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-an Thrylcarbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminopheny Oxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, Although an isonicotinoyl group etc. can be mentioned, it is not limited to these.

Examples of the acyloxy group which may have a substituent in Y ¹ include an acyloxy group having 2 to 20 carbon atoms, and specific examples include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, and a pentanoyloxy group. Group, trifluoromethylcarbonyloxy group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

Examples of the amino group which may have a substituent in Y ¹ include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group. Can be mentioned.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group , Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

  Dialkylamino groups include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples include, but are not limited to, piperazino groups.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- A biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like are exemplified, but the invention is not limited thereto.

  Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like are exemplified, but not limited thereto.

Examples of the phosphinoyl group which may have a substituent in Y ¹ include phosphinoyl groups having 2 to 50 carbon atoms, and specific examples thereof include dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group. Group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group, etc. Is not to be done.

Examples of the carbamoyl group which may have a substituent for Y ¹ include carbamoyl groups having 1 to 30 carbon atoms, and specific examples thereof include an N-methylcarbamoyl group, an N-ethylcarbamoyl group, and an N-propylcarbamoyl group. N-butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group Group, N-2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanoph Enylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl Group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group, and the like, but are not limited thereto.

Examples of the sulfamoyl group which may have a substituent in Y ¹ include a sulfamoyl group having 0 to 30 carbon atoms, and specific examples thereof include a sulfamoyl group, an N-alkylsulfamoyl group, and an N-arylsulfamoyl group. Group, N, N-dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like. It is not limited to.

Y ² may have a substituent, an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, As the arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group, the aforementioned alkenyl group that may have a substituent in R1, an alkyl group that may have a substituent, and a substituent An alkyloxy group that may have, an aryl group that may have a substituent, an aryloxy group that may have a substituent, a heterocyclic group that may have a substituent, and a substituent A good heterocyclic oxy group, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, a substituent An alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and a substituent. It is synonymous with the acyloxy group which may be sufficient, and the amino group which may have a substituent.

Examples of these substituents for Y ¹ and Y ² include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p-tolyloxy. Aryloxy groups such as methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups , Acyl groups such as methacryloyl group, methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino , Alkylamino groups such as cyclohexylamino group, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, methyl group, ethyl group, tert- Alkyl groups such as butyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclooctadecyl, phenyl, p-tolyl, xylyl, cumenyl, naphthyl Group, anthryl group, aryl group such as phenanthryl group, heterocyclic group such as furyl group, thienyl group, etc., hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, Amino group, nitro group, cyano group, tri Examples thereof include a fluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumum group, a dimethylsulfoniumyl group, and a triphenylphenacylphosphoniumyl group.
One or more of these substituents may be present, or one or more of these substituents may be present, and the hydrogen atom of these substituents may be further substituted with another substituent.

  Among these, the oxime ester photopolymerization initiator represented by the following general formula (4) or (5) is excellent in sensitivity and is preferable.

[Oxime ester photopolymerization initiator represented by formula (4)]
General formula (4)

The general formula (4) corresponds to the case where Z in the general formula (3) is a —CO— group and Y ³ is a Ph—S—Ph— group, and Y ⁴ to Y ^{6 each} represents a hydrogen atom or a substituent. An alkyl group or an aryl group which may be contained is preferable.

Furthermore the aryl group which may have a substituent as Y ^1, alkyl group having 1 to 20 carbon atoms that may have a substituent as Y ² is preferably a hydrogen atom as Y ⁴ to Y ⁶ .

The alkyl group that may have a substituent or the aryl group that may have a substituent in Y ^{4 to} Y ⁶ has the same meaning as the alkyl group or aryl group in Y ¹ and Y ² .

The alkyl group which may have a substituent or the substituent of the aryl group which may have a substituent has the same meaning as the substituent in Y ¹ and Y ² .

Y ² is preferably an alkyl group having 1 to 20 carbon atoms that may have a substituent, and the substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cycloalkyl group such as a cyclooctadecyl group;

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (4) include a photopolymerization initiator represented by the following chemical formula (4-1) or (4-2).

[Oxime ester photopolymerization initiator represented by general formula (5)]
General formula (5)

The general formula (5) corresponds to the case where Y ³ in the general formula (3) is a monovalent organic group including a carbazole group which may have a substituent, and Y ⁷ to Y ¹⁴ are Y ¹ and Y It is synonymous with the substituent in ² .

Further, the alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ¹ may have an alkyl group having 1 to 20 carbon atoms which may have a substituent as Y ² or a substituent. A good aryl group is preferably a hydrogen atom as Y ^{7 to} Y ¹⁴ , an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

  When Z in the general formula (5) is a direct bond, an oxime ester photopolymerization initiator represented by the following general formula (5a) is preferable.

"Oxime ester photopolymerization initiator represented by formula (5a)"
General formula (5a)

The general formula (5a) corresponds to the case where Z in the general formula (3) is a direct bond and Y ³ is a monovalent organic group including a carbazole group which may have a substituent. Y < ⁷ > -Y < ¹⁰ > and Y < ¹² > -Y < ¹³ > are hydrogen atoms.
Y ¹¹ is preferably a Y ¹⁵ —CO— group or a nitro group. Y ¹⁵ is synonymous with the substituent in Y ¹ and Y ² and is preferably an aryl group which may have a substituent. The Y ¹⁵ —CO— group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a methoxalyl group, which may further have a substituent. More preferred is a benzoyl group or nitro group which may have a substituent. Y ¹⁴ is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

Moreover, as a substituent in the benzoyl group which may have a substituent, a C1-C20 alkyl group or an alkyloxy group is preferable. Further, the alkyl group is preferably a methyl group or an ethyl group, and among the alkyloxy groups, a linear or branched chain having 2 to 18 carbon atoms and optionally interrupted by one or more —O— Monocyclic or condensed polycyclic alkyloxy groups are preferred, linear, branched, monocyclic or condensed polycyclic having 2 to 18 carbon atoms in Y ¹ and optionally interrupted by one or more —O— Synonymous with alkyloxy group.

Y ² is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms, and the substituent is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cycloalkyl group such as a cyclooctadecyl group; Further, an aryl group which may have a substituent is preferable, and as the substituent, an alkyl group having 1 to 20 carbon atoms which may further have a substituent, a methoxy group, an ethoxy group, or a tert-butoxy group Etc. are preferred.

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (5a) include photopolymerization initiators represented by the following chemical formulas (5a-1) to (5a-4).

"Oxime ester photopolymerization initiator represented by general formula (5b)"
When Z in the general formula (5) is a -CO- group, an oxime ester photopolymerization initiator represented by the following general formula (5b) is preferable.

General formula (5b)

The general formula (5b) corresponds to the case where Z in the general formula (3) is a -CO- group and Y ³ is a monovalent organic group including a carbazole group which may have a substituent. Is an oxime ester photopolymerization initiator.
Y ^{7 to} Y ¹³ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and Y ¹⁴ may have a substituent. A good aryl group is preferred.
As the substituent of the aryl group which may have a substituent, an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a methoxalyl group is preferable, and a benzoyl group is more preferable.

Specific examples of the oxime ester photopolymerization initiator represented by the general formula (5b) include photopolymerization initiators represented by the following chemical formulas (5b-1) to (5b-4).

  Commercially available products of these oxime ester compounds (D1) include 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01) from BASF. ), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02) is commercially available. In addition to these, oximes described in JP2007-210991A, JP2009-179619A, JP2010-037223A, JP2010-215575A, JP2011-020998A, and the like. It is also possible to use an ester photopolymerization initiator.

The content of the oxime ester compound (D1) is preferably 2 to 50 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 2 to 30 parts by weight from the viewpoint of photocurability and developability. preferable. When the amount is less than 2 parts by weight, the adhesion of the formed pattern to the base material is deteriorated. When the amount exceeds 50 parts by weight, there is a problem in developability or a decrease in brightness after heat treatment at 230 ° C.
(Acetophenone compound (D2))
An acetophenone compound (D2) can be used for the photopolymerization initiator of the photosensitive coloring composition for color filter of the present invention.
As the acetophenone compound, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1- ON, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, and the like.

By using the acetophenone compound (D2), the cross-sectional shape of the pattern becomes good even when the colorant concentration is high.

  The content of the acetophenone compound (D2) is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 2 to 30 parts by weight from the viewpoint of photocurability and developability. . When the amount is less than 1 part by weight, the cross-sectional shape of the formed pattern is deteriorated, and when it exceeds 50 parts by weight, there is a problem in developability or a decrease in brightness after heat treatment at 230 ° C.

Moreover, it is preferable to use together an acetophenone type compound (D2) and an oxime ester type compound (D1).

(Other photopolymerization initiators)
Other photopolymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; 2,4,6-trichloro-s-triazine, 2-phenyl-4 , 6-Bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1) -Yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho) 1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4′-methoxystyryl)- Triazine compounds such as 6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O- (acetyl) -N- (1-phenyl- Oxime ester compounds such as 2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, or 2,4,6-trimethylbenzoyldiphenyl Phosphine compounds such as phosphine oxide; 9,10-phenanthrenequinone, camphorquinone, A quinone compound such as tilanthraquinone; a borate compound; a carbazole compound; an imidazole compound; or a titanocene compound is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer (F)>
The colored composition of the present invention is characterized by containing a thioxanthone compound (F1) as a sensitizer for the purpose of further enhancing the reaction of the photopolymerization initiator and improving the cross-sectional shape of the pattern.
The thioxanthone-based compound can enhance the reaction of the photopolymerization initiator by exhibiting absorption in a wide range of 300 to 400 nm derived from the skeleton.

  The content of the sensitizer (F) is preferably 2 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (C) contained in the colored composition. From the viewpoint of photocurability and developability. 3 to 50 parts by weight is more preferable.

(Thioxanthone compound (F1)
Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone.
These compounds can be used alone or in combination of two or more at any ratio as required.

  Among these, 2,4-diethylthioxanthone is preferable because curing of the inside of the coating film is further promoted by enhancing the reaction of the photopolymerization initiator, and the cross-sectional shape of the pattern and pattern peeling are improved.

(Other sensitizers)
Other sensitizers that can be used in combination include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4. , 4′-tetra (t-butylperoxycarbonyl) benzophenone and other benzophenone compounds, chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2- typified by benzyl, camphorquinone and the like Diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives Polymethine dyes such as merocyanine derivatives and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetraarylmethane derivatives Benzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran Derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic lute Complex, Michler's ketone derivative, biimidazole derivative, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4 ′ -Diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone, and the like.
These sensitizers can be used alone or in combination of two or more at any ratio as required.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

<Antioxidant (G)>
The photosensitive coloring composition for color filters of this invention can contain antioxidant (G). Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the photosensitive coloring composition for color filters from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. The transmittance can be increased. In particular, when the colorant concentration of the photosensitive coloring composition is high, the amount of coating crosslinking component decreases, so the use of a highly sensitive crosslinking component and the increase in the amount of photopolymerization initiator are taken into account. This phenomenon is seen.
Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. In addition, the antioxidant used in the present invention preferably does not contain a halogen atom.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2′-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4′-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2′-thio -Bis- (6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-tert-butyl-4-hydroxy Phenyl) -propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1- Methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di ( , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy)- Benzene, phosphorous acid ethyl bis (2,4-di-tert- butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol, 2,2-bis {[3- (dodecylthio) -1-oxopropoxy] methyl} propane-1,3-diylbis [3- (Dodecylthio) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2′dihydroxy-4-methoxybenzophenone, 2,2′dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like can be mentioned. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass in 100% by mass of the solid content of the coloring composition because the spectral characteristics and sensitivity are good.

<Organic solvent (E)>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easy to form, an organic solvent (E) is included. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. Is preferred.

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the photosensitive coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the total mass of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

(Curing agent, curing accelerator)
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Of these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (eg imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl) -4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example tri Phenylphosphine ), Guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino) -S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can do. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

(Other additive components)
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

(Storage stabilizer)
Examples of the storage stabilizer include organic acids such as lactic acid and oxalic acid and methyl ether thereof, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant (A).

(Adhesion improver)
Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant (A) in the coloring composition.

(Multifunctional thiol)
The coloring composition of the present invention may contain a compound having two or more thiol (SH) groups as the polyfunctional thiol.
By using a polyfunctional thiol together with a photopolymerization initiator, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation, so the resulting colored composition is highly sensitive. It becomes. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable. Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu Arylamino) -4,6-dimercapto--s- triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tris thiopropionate, pentaerythritol tetrakis thiopropionate.

These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, and more preferably 1.0 to 50.0 parts by mass with respect to 100 parts by mass of the colorant (A). When the polyfunctional thiol content is less than 0.05 parts by mass, the effect of the chain transfer agent is small. .

<Method for producing colored composition>
The coloring composition of the present invention comprises a colorant (A), a resin-type dispersant (B) and, if necessary, a binder resin, an organic solvent (E), a pigment derivative, etc. Using various dispersing means such as the present roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor, finely disperse to obtain a colorant dispersion, and a binder is optionally added to the colorant dispersion. Resin, photopolymerizable monomer (C), photopolymerization initiator (D), sensitizer (F), antioxidant (G), polyfunctional thiol, ultraviolet absorber, polymerization inhibitor, storage stabilizer, It can be produced by mixing and stirring the organic solvent (E) and other components. In the photosensitive coloring composition containing two or more kinds of colorants, the colorant dispersions may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. . In addition, when the colorant has high solubility, specifically, it is highly soluble in the solvent used, and if it is dissolved by stirring and no foreign matter is confirmed, it is necessary to manufacture by finely dispersing as described above. There is no.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention is provided with a filter segment and / or a black matrix formed from the photosensitive coloring composition of the present invention on a substrate, and a general color filter includes, for example, a black matrix, And red, green and blue filter segments. The filter segment may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  As the base material of the color filter, glass plates such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, etc. with high transmittance for visible light, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, etc. A transparent substrate such as a resin plate or a reflective substrate can be used. These substrates may be subjected to appropriate pretreatments such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition and the like. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after forming the panel.

  If the BM is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the liquid crystal display panel can be further increased. As the BM, chromium, a chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. It is also possible to form TFTs on the transparent substrate or the reflective substrate in advance and use it as a driving substrate for a liquid crystal display device, and to form pixels on it. A color filter in which a filter segment is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, so that the aperture ratio can be greatly increased and the image quality and low power consumption of the color liquid crystal display device can be achieved. Can do.

  The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the color composition for color filter prepared as a color composition for solvent development type or alkali development type color filter is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It is applied so that the film thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

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

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

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

The organic EL display device includes a color filter and an organic light emitter, and can be applied to, for example, a passive drive type organic EL display device and an active drive type organic EL display device.
The white light source at this time is not limited, and any of a light source having a two-wavelength peak, a light source having a three-wavelength peak, and a light source having many peaks in the visible light region can be used.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  Moreover, the measuring method of the weight average molecular weight (Mw) of resin and the ammonium salt value of resin which has a cationic group in a side chain is as follows.

(Weight average molecular weight (Mw) of resin and resin type dispersant)
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. It is a weight average molecular weight (Mw).

<Acid value of resin and resin type dispersant>
The acid values of the resin and the resin-type dispersant were determined by potentiometric titration using a 0.1N potassium hydroxide / ethanol solution. The acid value of the resin and the resin-type dispersant indicates the acid value of the solid content.

<Amine value of resin-type dispersant>
The amine value of the resin-type dispersant was determined by potentiometric titration using a 0.1N hydrochloric acid aqueous solution, and then converted to an equivalent of potassium hydroxide. The amine value of the resin-type dispersant indicates the amine value of the solid content.

  Subsequently, the method for producing the resin-type dispersant and the method for producing the binder resin solution, the method for producing the finely divided pigment, the method for producing the pigment dispersion, and the method for producing the photopolymerizable monomer used in Examples and Comparative Examples The photosensitive red coloring composition and the method for producing the photosensitive green coloring composition will be described.

<Method for producing resin-type dispersant>
<Manufacture of basic resin type dispersant solution>
(Production of Basic Resin Type Dispersant Solution (B-1))
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of propylene glycol monomethyl ether acetate and heated to 110 ° C. while purging with nitrogen. A reaction vessel was charged with 38 parts of dimethylaminoethyl methacrylate, 40 parts of methyl methacrylate, 122 parts of 2-ethylhexyl methacrylate, and 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and stirred until uniform. . Thereafter, the reaction was carried out at the same temperature for 3 hours. In this way, a resin type dispersant solution having an amine value per solid content of 67.8 mg KOH / g and a weight average molecular weight of 9000 (Mw) was obtained.
After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was added to make the non-volatile content 40% by mass, and basic. A resin dispersant solution (B-1) was obtained.

(Production of basic resin type dispersant (B-2 to 4))
The basic resin type dispersant solution (B-2 to 4) is the same as the basic resin type dispersant solution (B-1) except that the composition and amount (parts by mass) shown in Table 1 are changed. Was synthesized.

<Production Method of Acidic Resin Type Dispersant Solution>
(Production of Acidic Resin Type Dispersant Solution (B-5))
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, as a first-stage synthesis, 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, and 40 parts of propylene glycol monomethyl ether acetate were charged. Replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 12 parts of 3-mercapto-1,2-propanediol, 0.2 part of 2,2′-azobisisobutyronitrile is divided into 20 portions. It was added every minute and reacted for 12 hours at 80 ° C., and it was confirmed by solid content measurement that 95% had reacted. Next, as a second stage synthesis, 30 parts of pyromellitic anhydride, 190 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. Then, the mixture was reacted at 120 ° C. for 7 hours. It was confirmed by titration that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed. Thus, a resin-type dispersant solution having an acid value per solid content of 42 mgKOH / g, a glass transition temperature (Tg) of 4.3 ° C., and a weight average molecular weight of 9,800 was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, propylene glycol monomethyl ether acetate was added to make the non-volatile content 40% by mass, and the acidic resin A mold dispersant solution (B-5) was obtained.

(Production of acidic resin type dispersant (B-6-9))
The acidic resin type dispersant solution (B-6 to 9) was synthesized in the same manner as the acidic resin type dispersant solution (B-5) except that the composition and amount (parts by mass) shown in Table 2 were changed. did.

<Method for producing binder resin solution>

(Adjustment of acrylic resin solution 1)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 19000. Obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, an acrylic resin solution 1 which is an active energy ray curable resin was prepared.

<Production method of fine pigment>

(Red refined pigment (PR-1))
C. I. Pigment Red 254 (PR254) ("Irga Fore Red B-CF" manufactured by BASF), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C for 8 hours. Kneaded. The mixture was poured into 2000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 100 parts of red refinement | purification processing pigments (PR-1).

(Red refined pigment (PR-2))
C. I. 100 parts of Pigment Red 177 (PR177) (“chromophthaled red A2B” manufactured by BASF), 800 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. . The mixture was added to 4000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, then at 80 ° C. for 24 hours. It dried and obtained 100 parts of red refinement | purification processing pigments (PR-2).

(Red refined pigment (PR-3))
C. I. 100 parts of Pigment Red 269 (PR269) (“Toner Magenta F8B” manufactured by Clariant), 800 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. The mixture was added to 4000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, then at 80 ° C. for 24 hours. It dried and obtained 100 parts of red refinement | purification processing pigments (PR-3).

(Yellow refined pigment (PY-1))
Using compound (1) as a raw material, compound (2) was obtained according to the synthesis method described in JP-A-2008-81566.

(Compound (1))
(Compound (2))

To 300 parts of methyl benzoate, 100 parts of compound (2), 108 parts of tetrachlorophthalic anhydride and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. The formation of the compound (3) and the disappearance of the starting compound (2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 120 parts of compound (3). As a result of mass spectrometry by TOF-MS, it was identified as compound (3).
(Compound (3))

  Subsequently, 100 parts of the obtained compound (3), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of yellow refined pigment (PY-1) were obtained.

(Yellow refined pigment (PY-2))
C. I. 100 parts of Pigment Yellow 139 (PY139) ("Irgafore Yellow 2R-CF" manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C for 6 hours. Kneaded. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A refined pigment (PY-2) was obtained.

(Yellow refined pigment (PY-3))
C. I. Pigment Yellow 139, C.I. I. Pigment Yellow 185 (PY185) (“Pariogen Yellow D1155” manufactured by BASF) was used in the same manner as in the production of the yellow colorant (PY-2) to obtain a yellow refined pigment (PY-3). It was.

(Green refined pigment (PG-1))
C. I. 200 parts of Pigment Green 58 (PG58) (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 195 parts of a green refined pigment (PG-1) was obtained.

(Green refined pigment (PG-2))
C. I. Pigment Green 7 (PG7) (Toyocolor Co., Ltd. “Lionol Green YS-07”) 500 parts, sodium chloride 500 parts, and diethylene glycol 250 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) at 120 ° C. Kneaded for 4 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. And 490 parts of a green refined pigment (PG-2) was obtained.

<Method for producing pigment dispersion>
(Pigment dispersion (DR-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a red pigment dispersion (DR-1) was produced.

Red refined pigment (PR-1): 12.0 parts Dye derivative (A-1): 2.0 parts Acidic resin type dispersant solution (B-7): 15.0 parts solvent
PGMAC: 71.0 parts (propylene glycol monomethyl ether acetate)

The dye derivative having the structure shown in Table 3 was used.

(Pigment dispersion (DR-2 to 7, DY-1 to 10, DG-1))
The pigment dispersion (DR-2-7, DR-2-7, DY-1 to 10 and DG-1) were obtained.

(Pigment dispersion (DG-2))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a red pigment dispersion (DG-2) was produced.

Green refined pigment (PG-1): 12.0 parts Basic resin type dispersant solution (B-1): 20.0 parts solvent
PGMAC: 68.0 parts (propylene glycol monomethyl ether acetate)

(Pigment dispersion (DG-3 to 5))
A pigment dispersion (DG-3 to 5) was obtained by the same production method as that of the pigment dispersion (DG-2) except that the basic resin dispersant solution was changed to the composition shown in the table.

<Method for producing photopolymerizable monomer>
(Photopolymerizable monomer (C2-1))
A five-neck reaction vessel with an internal volume of 1 liter is charged with 623 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix M-400 (manufactured by Toagosei Co., Ltd.)) and 44 g of hexamethylene diisocyanate at 60 ° C. It was made to react for 8 hours and the product containing polyfunctional urethane acrylate (1) was obtained. In the product, the proportion of the polyfunctional urethane acrylate (1) was 45% by weight, and a photopolymerizable monomer (C2-1) in which the remainder was occupied by another photopolymerizable monomer was obtained.
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.

(Photopolymerizable monomer (C2-2))
A five-neck reaction vessel with an internal volume of 1 liter was charged with 600 g of trimethylolpropane hexamethylene diisocyanate adduct (Coronate HL (manufactured by Tosoh Corporation)) and 950 g of pentaerythritol triacrylate, and reacted at 60 ° C. for 8 hours. A product containing a functional urethane acrylate (2) was obtained. In the product, the proportion of the polyfunctional urethane acrylate (2) was 80% by weight, and a photopolymerizable monomer (C2-2) in which the remainder was occupied by another photopolymerizable monomer was obtained.
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product.

<Method for producing photosensitive red coloring composition>
[Example 1]
(Photosensitive red coloring composition (RR-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (RR-1).

Colorant dispersion (DR-1): 40.0 parts Colorant dispersion (DY-1): 10.0 parts Acrylic resin solution 1: 12.3 parts Photopolymerizable monomer (C1): 1.5 (Toagosei Co., Ltd. “Aronix M309”)
Photopolymerization initiator (D1): 1.0 part ("OXE-02" manufactured by BASF)
Solvent: 35.2 parts (propylene glycol monomethyl ether acetate (PGMAC))

[Examples 2-102, Comparative Examples 1-9]
(Photosensitive coloring composition (RR-2 to 111)
Hereinafter, the pigment dispersion, the acrylic resin solution, the photopolymerizable monomer, the photopolymerization initiator, the sensitizer, the antioxidant, and the solvent were changed to the types and blending amounts (parts by weight) shown in Tables 8 to 13. Except for the above, photosensitive red coloring compositions (RR-2 to 111) were prepared in the same manner as the photosensitive red coloring composition (RR-1).

[Example 103]
(Photosensitive green coloring composition (RG-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (RG-1).

Colorant dispersion (DG-1): 40.0 parts Colorant dispersion (DY-9): 10.0 parts Acrylic resin solution 1: 12.3 parts Photopolymerizable monomer (C1): 1.5 (Toagosei Co., Ltd. “Aronix M309”)
Photopolymerization initiator (D1): 1.0 part ("OXE-02" manufactured by BASF)
Solvent: 35.2 parts (propylene glycol monomethyl ether acetate (PGMAC))

[Examples 104 to 168, Comparative Examples 10 to 16]
(Photosensitive coloring composition (RG-2 to 73)
Hereinafter, the pigment dispersion, the acrylic resin solution, the photopolymerizable monomer, the photopolymerization initiator, the sensitizer, the antioxidant, and the solvent were changed to the types and blending amounts (parts by weight) shown in Tables 14 to 17. Except for the above, a photosensitive green coloring composition (RG-2 to 73) was prepared in the same manner as the photosensitive green coloring composition (RG-1).

Abbreviations in Tables 8 to 17 are described below.
<Photopolymerizable Monomer Monomer>
(Photopolymerizable monomer (C1))
C1-1 (“Aronix M-309” manufactured by Toagosei Co., Ltd.)
(Chemical Formula _{6) :( CH 2 = C (} -H) -C (= O) -O-CH 2) 3 -CCH 2 CH 3
・ C1-2 (“Aronix M-310” manufactured by Toagosei Co., Ltd.)
(Chemical Formula _{7) :( CH 2 = CH-} C (= O) - (O-C 3 H 6) -O-CH 2) 3 -CCH 2 CH 3
・ C1-3 (“Aronix M-350” manufactured by Toagosei Co., Ltd.)
(Chemical formula _{8) :( CH 2 = CH-} C (= O) - (O-C 2 H 4) -O-CH 2) 3 -CCH 2 CH 3
C1-4 (“Sanester TMP” manufactured by Sanshin Chemical Industry Co., Ltd.)
(Formula _{9) :( CH 2 = C (} -CH 3) -C (= O) -O-CH 2) 3 -CCH 2 CH 3
(Photopolymerizable monomer (C2))
・ C2-3 (Shin Nakamura Chemical Co., Ltd. “UA-1100H”)
・ C2-4 (KSM-15N “KSM-15N”)
(Other photopolymerizable monomers)
C-1 (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
・ C-2 (“Aronix M-520” manufactured by Toagosei Co., Ltd.)
<Photopolymerization initiator>
(Oxime ester compound (D1))
D1-1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)
("IRGACURE OXE 02" manufactured by BASF)
D1-2: Compound having the structure of the following chemical formula (5b-1)

Chemical formula (5b-1)
D1-3: Compound having the structure of the following chemical formula (5b-2)

Chemical formula (5b-2)
(Acetophenone compound (D2))
・ D2-1 ("IRGACURE 369" manufactured by BASF
・ D2-2 ("IRGACURE 907" manufactured by BASF
(Other photopolymerization initiators)
D-1 (acylphosphine oxide compound, “IRGACURE 819” manufactured by BASF)
<Sensitizer>
(Thioxanthone compound (F1))
・ F1-1 (“KAYACURE DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
(Other sensitizers)
F-1 (benzophenone-based compound, “EAB-F” manufactured by Hodogaya Chemical)
(Antioxidant (G))
・ G-1 ("IRGANOX 1010" manufactured by BASF)
・ G-2 (“ADEKA STAB AO412-S” manufactured by ADEKA)

<Evaluation of photosensitive coloring composition for color filter>
Using the obtained photosensitive coloring composition, development speed, pattern peeling, cross-sectional shape, chemical resistance, and heat resistance were evaluated by the following methods. The results are shown in Tables 18-25.

[Development speed evaluation]
A substrate obtained by coating the photosensitive coloring composition on a 100 mm × 100 mm, 1.1 mm thick glass substrate with a spin coater at a rotation speed of 3 μm after drying under reduced pressure is dried at 70 ° C. for 20 minutes. Thereafter, spray development was performed using an aqueous sodium carbonate solution at 23 ° C., and developability was evaluated in three stages. The alkali developer is 0.15% by weight of sodium carbonate, 0.05% by weight of sodium hydrogen carbonate, 0.1% by weight of an anionic surfactant (“PEX NBL” manufactured by Kao Corporation) and 99.7% by weight of water What was used.
The developability evaluation was determined according to the following criteria.
Note that ◎, ○, and Δ are practical levels, and × is a level that is not suitable for practical use.

◎: Can be completely removed within 40 seconds ○: Over 40 seconds but can be completely removed within 60 seconds Δ: Over 60 seconds but can be completely removed within 80 seconds ×: Over 80 seconds Can not be completely removed

[Pattern peeling evaluation]
The photosensitive coloring composition was coated on a 100 mm × 100 mm, 0.7 mm thick glass substrate using a spin coater, and after drying under reduced pressure, a 3.0 μm coating film was obtained. Next, using an ultrahigh pressure mercury lamp, ultraviolet rays were exposed through a photomask having a stripe pattern of 100 μm width (pitch 200 μm). Thereafter, this substrate was developed by a shower developing method using a 00.2 wt% sodium carbonate aqueous solution at 23 ° C. as a developer at a developer pressure of 0.1 mPa and heated at 230 ° C. for 20 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive composition, and this was set as an appropriate development time. The pattern in the formed 100 μm photomask portion was evaluated by observation using an optical microscope. The rank of evaluation is as follows.

○: Good without peeling or chipping: Good level △: No peeling but partial chipping: Inferior to ○, but practical level ×: Many peelings and chipping: Unsuitable level for practical use

[Cross-sectional shape evaluation]
-Initial development substrate The cross section of the pattern at the 100 µm photomask portion formed for evaluation of pattern peeling was observed and evaluated using an electron microscope. This substrate was used as an initial development substrate. The pattern cross section has good forward taper. The rank of evaluation is as follows.

◎: Forward tapered shape with gentle cross section ○: Cross section with forward tapered shape ×: Cross section with reverse tapered shape

<2> Development Resistance Evaluation Substrate Subsequently, a pattern was prepared in the same manner as the pattern peeling evaluation pattern, but with regard to the development time, the pattern was formed without any residual development for each coating film with the photosensitive composition. The development was further performed for 30 seconds from the shortest possible time. The pattern in the formed 100 μm photomask portion was similarly observed and evaluated using an optical microscope. The rank of evaluation is as follows.

◎: Forward tapered shape with gentle cross section ○: Cross section with forward tapered shape ×: Cross section with reverse tapered shape

[Evaluation of chemical resistance]
<NMP resistance test evaluation 1>
About the stripe pattern formed for the above-mentioned pattern peeling evaluation, the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured by a microspectrophotometer (manufactured by Olympus Optical Co., Ltd.). “OSP-SP100”). Furthermore, the substrate on which the stripe pattern is formed is immersed in NMP for 15 minutes, washed with water, dried, and then the chromaticity with a C light source ([L * (2), a * (2), b * (2)]) The color difference ΔE * ab was determined by the following calculation formula and evaluated in the following four stages.

ΔE * ab = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )

A: ΔE * ab is less than 1.0
○: ΔE * ab is 1.0 or more and less than 1.5
Δ: ΔE * ab is 1.5 or more and less than 3.0 ×: ΔE * ab is 3.0 or more

<NMP resistance test evaluation 2>
The board | substrate with which the stripe pattern formed for the said pattern peeling evaluation was formed was immersed in NMP for 15 minutes, and after water-washing and drying, the external appearance of the green pixel was observed with the following method.
The surface of 50 pixels was observed using a metal microscope “BX60” (manufactured by Olympus System) with 25 μm × 100 μm as one pixel. The magnification was 500 times, and the number of pixels in which cracks occurred due to reflection was counted. Evaluation was performed in the following four stages.

◎: No cracking of 50 pixels ○: Number of cracking pixels 1 or more, less than 10 Δ: Number of cracking pixels 10 or more, less than 30 ×: Number of cracking pixels 30 or more

<Heat resistance evaluation>
The photosensitive coloring composition is applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater at a rotation speed of 3 μm after drying under reduced pressure, and then dried at 70 ° C. for 20 minutes. Then, the coated substrate was produced by heating and cooling at 230 ° C. for 20 minutes. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 3 hours, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following four stages.

ΔE * ab = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
A: ΔE * ab is less than 0.5
○: ΔE * ab is 0.5 or more and less than 1.0
Δ: ΔE * ab is 1.0 or more and less than 2.0 ×: ΔE * ab is 2.0 or more

  As shown in Tables 18-25, the photosensitive coloring composition in which a photopolymerizable monomer contains the at least 1 sort (s) of photopolymerizable monomer (C1) chosen from General formula (1) and (2). When used, good developability was exhibited even when the content of the colorant was 40% by weight or more based on the weight of the total solid content of the photosensitive coloring composition for color filter. The pattern cross-sectional shape was also good.

In addition, when the content of the colorant is 45% by weight or more, when the glass transition temperature (Tg) of the resin-type dispersant (B) is in the range of 20 to 100 ° C., both pattern peeling and chemical resistance are good. Results are shown.

When the photopolymerizable monomer contained the polyfunctional urethane acrylate (C2), the chemical resistance was significantly improved when the content of the colorant was high.

Regarding the photopolymerization initiator, the use of the oxime ester compound (D1) improved the pattern peeling, and when the acetophenone compound (D2) was used in combination, the development resistance of the pattern cross-sectional shape was improved. In addition, when the content of the colorant is high, the pattern cross-sectional shape is generally often deteriorated, but the development resistance of the pattern cross-sectional shape can be improved by containing the thioxanthone compound (D) as a sensitizer. I was able to improve.

  Moreover, when content of the coloring agent was high, heat resistance was improved by using an antioxidant.

From the above results, the photosensitive coloring composition of the present application can provide a colored film having excellent pattern shape and good chemical resistance even when the content of the colorant is high, and thereby has high color reproducibility. A color filter could be formed.
That is, the photosensitive coloring composition of the present invention is not only a color liquid crystal display device but also a color imaging device, a quantum dot display device, and an organic EL display device when a thin film and a wide color gamut are required. It can be preferably used.

Claims (8)

Photosensitive for color filters containing a colorant (A), a resin-type dispersant (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and an organic solvent (E). It is a coloring composition, Comprising: Content of the said coloring agent (A) is 40 weight% or more in 100 weight% of total solid content of the photosensitive coloring composition for color filters, and the said photopolymerizable monomer ( A photosensitive coloring composition for a color filter, wherein C) contains at least one photopolymerizable monomer (C1) selected from the following general formulas (1) and (2).
(Formula _{1) :( CH 2 = C (} -R) -C (= O) -O-CH 2) 3 -CCH 2 CH 3
(Formula _{2) :( CH 2 = C (} -R) -C (= O) - (O-R 1) n-O-CH 2) 3 -CCH 2 CH 3
[Wherein, R represents H or CH ₃ , R ₁ represents C ₂ H ₄ or C ₃ H ₆ , and n = 1 or 2. ] The photosensitive coloring composition for a color filter according to claim 1, wherein the resin-type dispersant (B) has a glass transition temperature (Tg) of 20 to 100 ° C. The photosensitive coloring composition for a color filter according to claim 1 or 2, wherein the photopolymerizable monomer (C) further contains a polyfunctional urethane acrylate (C2). The photosensitive coloring composition for a color filter according to any one of claims 1 to 3, wherein the photopolymerization initiator (D) contains an oxime ester compound (D1). The photosensitive coloring composition for color filters according to any one of claims 1 to 4, wherein the photopolymerization initiator (D) contains an acetophenone compound (D2). Furthermore, it contains a sensitizer (F), and the sensitizer (F) contains a thioxanthone compound (F1). The color filter photosensitivity according to any one of claims 1 to 5, Coloring composition. Furthermore, antioxidant (G) is contained, The photosensitive coloring composition for color filters of any one of Claims 1-6 characterized by the above-mentioned. A color filter comprising a filter segment formed from the photosensitive coloring composition for a color filter according to any one of claims 1 to 7 on a substrate.