JP6984123B2 - Photosensitive coloring compositions and color filters for color filters - Google Patents

Description

The present invention is a coloring composition for a color filter used for manufacturing a color filter used in a color liquid crystal display device, a color image pickup element, a quantum dot display device, an organic EL display device, and the like, and is formed by using the coloring composition. It relates to a color filter including a filter segment.

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

In the color liquid crystal display device (A), the liquid crystal layer sandwiched between the two polarizing plates passes through the second polarizing plate by controlling the degree of polarization of the light passing through the first polarizing plate. It is a display device that displays by controlling the amount of light, and the type using a twisted nematic (TN) type liquid crystal display is the mainstream. The liquid crystal display device can display colors by providing a color filter between the two polarizing plates. Therefore, liquid crystal display devices are being developed for TV and personal computer monitor applications.

Other typical liquid crystal display methods include an in-plane switching (IPS) method in which a pair of electrodes are provided on one substrate and electrolysis is applied in a direction parallel to the substrate, and negative dielectric anisotropy. Vertical alignment (VA) method that vertically orients a nematic liquid crystal display with a Etc., and each has been put into practical use.

Generally, a color filter has a fine band (striped) shape composed 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 crossed each other, or 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 arranged in a predetermined arrangement for each hue. Recently, in addition to the red filter layer (R), the green filter layer (G), and the blue filter layer (B), a filter segment composed of a yellow filter layer (Y) has also been used.

A transparent electrode for driving a liquid crystal is generally formed on a color filter used in a color liquid crystal display device by vapor deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is formed on the transparent electrode. It is formed. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to carry out the forming step at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher. Therefore, as a method for manufacturing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is currently the mainstream.

As the synthetic white light source of the organic EL display device (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 large number of peaks in the visible light region, and an organic EL material that emits light in each color is used. Synthetic white light is obtained by mixing or layering.

Since the organic EL display device can directly control the light source of the pixel on / off by using a TFT (thin film transistor) or the like, it is possible to display black by extinguishing the light emission of the designated pixel. Therefore, the polarizing plate used in the liquid crystal display device is not required in the light emitting device, and it is not necessary to control by the liquid crystal body. Therefore, the amount of transmitted light in the display device is increased, and the energy consumption can be significantly reduced by turning off the light emitting device in the 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 that solves the problems in such a liquid crystal display device, for example, a product such as "XEL-1" manufactured by Sony Corporation has already been put on the market. (See, for example, 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 high contrast ratio, wide viewing angle, fast response speed, and wide color reproducibility as described above. Above all, in order to obtain a high color reproduction range, 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 mobile terminals. There is an increasing demand for high color reproducibility and high brightness in color filters in which filter segments of 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 increase the film thickness. In the method of increasing the content of the colorant, the decrease in the resin and the photopolymerizable compound as the curing material causes problems such as deterioration of developability, deterioration of pattern shape, and deterioration of coating film resistance. also. In the method of increasing the film thickness, the exposure light does not reach the bottom of the film, and problems such as poor pattern shape are likely to occur. Furthermore, there is an increasing demand for thinning of color display devices, and there is a tendency to reduce the film thickness. Therefore, in a photosensitive coloring composition containing a colorant at a high concentration, the developability is improved and the shape is improved. Improvement of improvement and improvement of coating film resistance are required.

In order to improve the coating resistance, it is necessary to increase the sensitivity of the photosensitive coloring composition. Generally, (1) imparting a reactive double bond to the binder resin, and (2) photopolymerizable single amount. The body is selected or increased, and (3) the high-sensitivity photopolymerization initiator is selected or increased.

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

Japanese Unexamined Patent Publication No. 2005-100921

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

As a result of diligent 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 weight of the total solid content of the photosensitive coloring composition for a color filter. However, it has been found that by using a specific photopolymerizable monomer (C), it is possible to have good developability and pattern shape and sufficient coating resistance, and this finding has been made. The present invention was 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). In the photosensitive coloring composition for a color filter, the content of the colorant (A) is 40% by weight or more based on the weight of the total solid content of the photosensitive coloring composition for a color filter, and the light is used. A photosensitive coloring composition for a color filter, wherein the polymerizable monomer (C) contains at least one photopolymerizable monomer (C1) selected from the following general formulas (1) and (2). Regarding things.
(General formula 1): (CH ₂ = C (-R) -C (= O) -O-CH ₂ ) _3- CCH ₂ CH ₃
(General formula 2): (CH ₂ = C (-R) -C (= O)-(OR ₁ ) n-O-CH ₂ ) _{3- CCH 2} CH ₃
[In the formula, 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 photosensitive coloring composition for a color filter, 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-based compound (D2).

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

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

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

According to the photosensitive coloring composition for a color filter of the present invention, even when a colorant is contained in a high concentration, the developability and the pattern shape are good by using the specific photopolymerizable monomer (C). It is possible to form a color filter having sufficient coating resistance.

Hereinafter, the present invention will be described in detail.
In the present application, when "(meth) acrylate", "(meth) acrylic acid", or "(meth) acrylamide" is described, "acrylate and / or methacrylate", respectively, unless otherwise specified. It shall represent "acrylic acid and / or methacrylic acid" or "acrylamide and / or methacrylamide".
Further, "CI" listed 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 combination of two or more. Among the pigments, pigments having high color development and high heat resistance are preferable, and organic pigments are usually used. Hereinafter, specific examples of organic pigments that can be used in the photosensitive coloring composition for a color filter of the present invention are shown by color index numbers.
Further, as the colorant (A), a dye can be contained within a range that does not reduce the heat resistance.

Examples of the red pigment 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, 179, 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, from the viewpoint of lightness and coloring power, azo pigments, diketopyrrolopyrrole-based, anthraquinone-based, quinophthalone-based, isoindoline-based, perinone-based, perylene-based, and benzimidazolone-based dyes can be mentioned. Specifically, C.I. I. Pigment Red 176, 177, 179, 242, 254, 269 are preferred.

Examples of the blue pigment 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 can be mentioned. Among these, from the viewpoint of lightness and coloring power, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, more preferably C.I. I. Pigment Blue 15: 6. Further, the aluminum phthalocyanine pigments and the like described in JP-A-2004-333817, Patent No. 4893859 and the like can also be used, and the present invention is not particularly limited thereto.

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 lightness and coloring power, C.I. I. Pigment Green 7, 36, 58, 59, 62, 63. Further, the zinc phthalocyanine pigments and the like described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-070342 and the like can also be used, and the present invention is not particularly limited thereto.

Examples of the yellow pigment 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, 173, 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 can be mentioned. Among these, from the viewpoint of lightness and coloring power, C.I. I. Pigment Yellow 138, 139, 150, 185, 231.

Examples of the purple pigment 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 can be mentioned. Among these, from the viewpoint of lightness 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 and the like. Above all, from the viewpoint of lightness and coloring power, C.I. I. Pigment Oranges 38, 43 and 64 are preferred.

Inorganic pigments include barium sulfate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine, dark blue, chromium oxide green, cobalt green, amber, and titanium black. , Synthetic iron black, titanium oxide, metal oxide powder such as iron tetroxide, metal sulfide powder, metal powder and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness.

"dye"
The photosensitive coloring composition for a color filter of the present invention may contain a dye within a range that does not reduce heat resistance.
The dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, methine dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, and thiazines. Dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, oxazine dyes, perylene dyes, diketopyrrolopyrrole dyes, quinacridone dyes, anthancelon dyes, isoindrinone Examples thereof include, but are not limited to, dyes, isoindrin dyes, indanthron dyes, coumarin dyes, quinacridone dyes, pyranthron dyes, flavanthron dyes, and perinone dyes.

The photosensitive coloring composition for a color filter of the present invention contains the colorant (A) and can form a filter segment of each color constituting the 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 a color filter. If the content is less than 40% by weight, the film thickness will be thicker than the general film thickness range (about 1.0 to 3.0 μm) when producing a color filter with high color reproducibility. 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, the pattern is more likely to be chipped in the developing process as compared with the case where the content of the colorant in the coating film is large, which is not preferable.

(General formula 1): (CH ₂ = C (-R) -C (= O) -O-CH ₂ ) _3- CCH ₂ CH ₃
(General formula 2): (CH ₂ = C (-R) -C (= O)-(OR ₁ ) n-O-CH ₂ ) _{3- CCH 2} CH ₃
[In the formula, R represents H or CH ₃ , R ₁ represents C ₂ H ₄ or C ₃ H ₆ , and n = 1 or 2. ]

(Pigment miniaturization)
When the colorant used in the coloring composition of the present invention is a pigment, it can be made finer by a salt milling treatment or the like. The average primary particle size determined by the TEM (transmission electron microscope) of the pigment is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse it in an organic solvent, and if it is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For this reason, the more preferable average primary particle size is in the range of 10 to 70 nm.

Salt milling treatment is a machine that heats a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, and a 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 acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

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 price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment.

The water-soluble organic solvent has a function of wetting 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 used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. 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, most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

When the pigment is subjected to salt milling treatment, a resin may be added if 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 preferably solid at room temperature, water-insoluble, 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 colorant-affinitive moiety having a property of adsorbing to a colorant or a dye derivative added for improving dispersibility, and a moiety compatible with the colorant carrier. , It works by adsorbing to the additive colorant and stabilizing the dispersion in the colorant carrier. The colorant carrier refers to components excluding colorants 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 resin, polyester resin, polyether resin, urethane resin, silicon resin, epoxy resin, and vinyl acetate resin.

Examples of the acidic substituent include a phosphoric acid group, a sulfonic acid group, and a carboxyl group. Further, a trimellitic acid and / or a partially esterified pyromellitic acid is preferably used. Further, in some cases, the 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. Among them, it is preferable to have two or more carboxyl groups in one molecule. A dispersant having two or more carboxyl groups in one molecule is a colorant because it has more adsorbing groups to the colorant than a resin-type dispersant having 0 or 1 carboxyl groups in one molecule. It is preferable because it has a strong function of stabilizing dispersion in the carrier, the polarity of the dispersant is increased, and higher dispersion stability can be ensured.

As the resin type dispersant having a basic group, a nitrogen atom-containing graft copolymer or a nitrogen atom-containing acrylic having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in the side chain is used. A block copolymer and a urethane polymer dispersant are preferable.

The resin-type dispersant preferably has a main chain or terminal of a linear resin, a main chain or side chain of a comb-shaped resin, or randomly having an acidic substituent, an aromatic group, or the like. Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, and poly ( An amide formed by the reaction of a lower alkyleneimine) with 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. Polymer compounds, polyester-based, modified poly (meth) acrylates, ethylene oxide / propylene oxide adducts, phosphoric acid esters and the like are used. These can be used alone or in admixture of two or more, but are not necessarily limited to these.

As the site of the resin-type dispersant of the present invention having a high affinity for the dispersion medium, at least one polymer unit selected from polyester, polyether, and poly (meth) acrylate is preferable.

For example, as the polyester, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentylglycol, 1,6-hexanediol , 1,4-bis (hydroxymethyl) cyclohesane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylol ethane, trimethylol propane, 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 , Glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohex Examples thereof include polyester polyols obtained by co-condensation with one or more carboxylic acids such as satricarboxylic 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) cyclohesane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylol ethane, trimethylol propane, 2,2,4-trimethyl-1,3-pentanediol , Glycerin or alcohols such as hexanetriol and various (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl glycidyl ether. Examples thereof include modified polyether polyols obtained by ring-opening polymerization.

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

Commercially available resin-type pigment dispersants having an acidic group include, for example, Solsparse 3000, Solspurs 21000, Solsperse 26000, Solsperse 36600, Solsperse 41000, Solsperse 44000, Solsperse 46000, Solsperse 55000, (manufactured by Abyssia). 108, Disperbic 110, Disperbic 111, Disperbic 112, Disperbic 116, Disperbic 142, Disperbic 180, Disperbic 2001, (manufactured by BIC Chemie); Disparon 3600N, Disparon 1850 (manufactured by Kusumoto Kasei); PA111 ( Ajinomoto Fine Techno Co., Ltd.); EFKA4401, EFKA4550 (manufactured by Fuka Additives Co., Ltd.) and the like, but are not limited thereto.

Commercially available resin-type dispersants having a basic group include 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, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc., SOLPERSE-3000, 9000, 13000, 13240, 13650, 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., manufactured by BASF Japan. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. , PB411, PB821, PB822, PB824 and the like.

Among these, the photosensitive coloring composition for a color filter in the present invention preferably contains a resin-type dispersant (B) having a glass transition temperature (Tg) of 20 to 100 ° C. .. As a result, it is possible to obtain good developability and excellent coating film resistance. If the Tg is lower than 20 ° C., the pattern may be chipped or the chemical resistance of the coating film may be deteriorated. When Tg is higher than 100 ° C., the developability is significantly deteriorated. In particular, when the temperature is in the range of 35 to 95 ° C., the developability of the coating film and the chemical resistance are well balanced, which is more preferable.

The glass transition temperature in the present invention indicates a value calculated from the Tg of each homopolymer to be copolymerized by the following Fox formula.
Fox formula 1 / Tg = W1 / Tg1 + W2 / Tg2 + ... + Wn / Tgn
W1 to Wn indicate the weight fraction of the monomer used, and Tg1 to Tgn indicate the glass transition temperature (unit: absolute temperature "K") of the homopolymer of the monomer.
For the Tg of the main homopolymer used in the calculation, the numerical values described in the Polymer Handbook can be used. The numerical values are illustrated below.
ε-Caprolactone: -60 ° C (213K)
Ethyl acrylate: -22 ° C (251K)
t-Butyl acrylate: 41 ° C (314K)
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 (523K)

<Other dispersants>
When the colorant is dispersed in the colorant carrier, other dispersants other than the resin type dispersant (B) such as a dye derivative and a surfactant may be appropriately contained. Since these dispersants have a great effect of preventing the reaggregation of the colorant after dispersion, the coloring 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 in which an organic pigment, anthraquinone, acrydone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimidemethyl group which may have a substituent. The ones described in Japanese Patent Publication No. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-1469, etc. can be used, and these can be used. It can be used alone or in combination of two or more.

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

(Surfactant)
Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalline sulfonate, and sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

The blending 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). If the blending amount of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the added effect, and if it is more than 55 parts by mass, the excess dispersant may adversely affect the dispersion.

<Binder resin>
The photosensitive coloring composition for a color filter of the present invention may contain a binder resin as a material for dispersing, dyeing, or permeating a colorant. Examples of the binder resin include thermoplastic resins and thermosetting resins. 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. When used in the form of an alkali-developable photosensitive coloring composition, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic substituent. Further, 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 resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like.

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

Examples of the vinyl-based alkali-soluble resin obtained by copolymerizing the ethylenically unsaturated monomer containing an acidic substituent include a resin having an acidic substituent such as a carboxyl group and a sulfone group. Specifically, the alkali-soluble resin includes an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, and an ethylene / (meth) acrylic acid copolymer. Alternatively, isobutylene / (anhydrous) maleic acid copolymer and the like can be mentioned. Among them, an acrylic resin having an acidic substituent and at least one resin selected from a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, are preferably used because they have high heat resistance and transparency. Be done.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an ethylenically unsaturated double bond is introduced by the methods (i) and (ii) shown below.

[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 with one or more other types of monomers can be used. , A carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added and reacted, and a polybasic acid anhydride is reacted with the generated hydroxyl group to form an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce it.

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) acrylates, which may be used alone or in combination of two or more. From the viewpoint of reactivity with unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted products. Examples thereof include monocarboxylic acids, which may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as increasing the number of carboxyl groups, use tricarboxylic acid anhydride such as trimellitic acid anhydride or tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride to use the remaining anhydride. It is also possible to hydrolyze the group. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bond 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 with one or more other monomers. There is a method of adding an ethylenically unsaturated monomer having an epoxy group to a part of the 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 by copolymerizing with another unsaturated monobasic acid monomer having a carboxyl group or another monomer. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the isocyanate group of the ethylenically unsaturated monomer having an isocyanate group.

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-hydroxyalkylmethacrylates such as hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate can be mentioned, and these may be used alone or in combination of two or more. It may be used in combination. Further, a polyether mono (meth) acrylate obtained by superpolymerizing the hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, poly γ-valerolactone, poly ε-caprolactone, and / or Polyester mono (meth) acrylate to which poly 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl methacrylate or glycerol methacrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

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

In order to preferably disperse the colorant, 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.

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

Since the resin has good film forming properties and various resistances, it is preferable to use the resin in an amount of 20 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant, 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 to 150 parts by weight. The chromaticity region can be expanded by the composition ratio of such a pigment.

<Photopolymerizable monomer (C)>
The photosensitive coloring composition of the present invention contains (C1) as a photopolymerizable monomer. Generally, when the content of the colorant is high in the photosensitive coloring composition, the developability of the coating film deteriorates, but by containing the photopolymerizable monomer (C1), good developability can be obtained and the color can be obtained. The productivity of the filter is improved. This is because the photopolymerizable monomer (C1) has three unsaturated bond groups in the molecule even though the molecular weight is in the range of 250 to 650, which is a relatively low molecular weight, and is double. It is characterized by a high number of bond groups. This makes it possible to achieve both good developability and high exposure sensitivity even when the content of the colorant is high. On the other hand, looking at the crosslinked structure formed by the photopolymerizable monomer (C1), it is compared with the photopolymerizable monomer having more unsaturated bond groups in the molecule and having a large molecular weight. It has a cross-linked structure with less entanglement. Therefore, problems such as chipping of the pattern during development occur, but when the content of the colorant is high, the development resistance of the colorant itself is high, so that it is particularly preferable from the viewpoint of achieving both good developability and patterning property. Can be used.
(Photopolymerizable monomer (C1))
The photosensitive coloring composition for a color filter of the present invention contains at least one photopolymerizable monomer (C1) selected from the following formulas (1) and (2).
(General formula 1): (CH ₂ = C (-R) -C (= O) -O-CH ₂ ) _3- CCH ₂ CH ₃
(General formula 2): (CH ₂ = C (-R) -C (= O)-(OR ₁ ) n-O-CH ₂ ) _{3- CCH 2} CH ₃
[In the formula, R represents H or CH ₃ , R ₁ represents C ₂ H ₄ or C ₃ H ₆ , and n = 1 or 2. ]

Commercially available monomers represented by the general formula (1) include Aronix M-309 manufactured by Toa Synthetic Co., Ltd., SR351S manufactured by Tomoe Kogyo Co., Ltd., A-TMPT manufactured by Shin Nakamura Chemical Industry Co., Ltd., and Viscoat # manufactured by Osaka Organic Chemical Industry Co., Ltd. 295, SR350 manufactured by Tomoe Kogyo Co., Ltd., Sun Ester TMP manufactured by Sanshin Chemical Industry Co., Ltd. and the like can be mentioned.

Commercially available monomers represented by the general formula (2) include Aronix M-310, Aronix M-321, Aronix M-350, Aronix M-360, Dycel Ornex TMPEOTA, and Tomoe Kogyo. SR454 manufactured by Osaka Organic Chemical Industry Co., Ltd., Viscoat # 360 manufactured by Osaka Organic Chemical Industry Co., Ltd. and the like can be mentioned.

These photopolymerizable monomers (C1) can be used alone or in admixture of two or more at any ratio, if necessary.

(Photopolymerizable monomer (C2))
The photosensitive coloring composition for a color filter of the present invention can contain a polyfunctional urethane acrylate (C2). When the colorant content of the photosensitive coloring composition is high, the amount of the cross-linking component of the coating film is small, so that the chemical resistance of the coating film may deteriorate. High resistance can be imparted.

The structure of the polyfunctional urethane acrylate (C2) is not limited, and it has a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or an alcohol having a polyfunctional isocyanate reacted with the polyfunctional isocyanate and further having a hydroxyl group. Examples thereof include polyfunctional urethane acrylate obtained by reacting (meth) acrylate.

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, and ditrimethylol propanetri (meth). Meta) 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 Examples thereof include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, and a hydroxyl group-containing polyol polyacrylate.

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

Further, although the structure of the alcohol is not limited, it is preferable to use a polyhydric alcohol because the degree of cross-linking of the cured coating film is high and the coating film resistance is improved. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

The photopolymerizable monomer (C2) that can be used in the coloring composition of the present invention includes, in addition to the above-mentioned polyfunctional urethane acrylate, when reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, or an alcohol. When reacting with a polyfunctional isocyanate and further reacting with a (meth) acrylate having a hydroxyl group, a component having a double-bonding group, which was not obtained as a polyfunctional urethane acrylate, may be contained as another monomer.

Commercially available polyfunctional acrylates can also be used for the optical monomer (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, KAYAD manufactured by Nippon Kayaku Co., Ltd. KAYARAD DPHA-40H, KAYARAD UX-5005, Toagosei Aronix M-1100, Aronix M-1200 and Shin Nakamura Chemical Industry U-6LPA, UA-1100H, U-15HA, UA-160TM, UA-122P , UA-7100, UA-W2A, and KUA-4I, KUA-6I, KUA-9N, KUA-10H manufactured by KSM, etc. 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 contained. Examples of other photopolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 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 ( Meta) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, Various acrylics such as dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylic acid ester, and epoxy (meth) acrylate. Acid and methacrylic acid esters, (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 and the like, but are not necessarily limited to these.
These photopolymerizable compounds may be used alone or in admixture 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)>
To the colored composition of the present invention, a photopolymerization initiator (D) is added to cure the composition by irradiation with ultraviolet rays and to form a filter segment by a photolithography method, and the photosensitive is solvent-developed or alkaline-developed. It can be prepared in the form of a coloring composition.

(Oxime ester compound (D1))
The photosensitive coloring composition for a color filter of the present invention can contain an oxime ester compound (D1) as a photopolymerization initiator.
When the oxime ester compound (D1) absorbs ultraviolet rays, the NO bond of oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of 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, but the oxime ester compound is preferably used because it has high quantum efficiency. To. More preferably, when it has a carbazole group, it can be a composition having excellent lightness and color purity. Particularly preferred is an oxime ester-based photopolymerization initiator represented by the general formula (3).

一般式（３）において、
Ｙ^１は、水素原子、または置換基を有しても良い、アルケニル基、アルキル基、アルキルオキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アシルオキシ基、アミノ基、ホスフィノイル基、カルバモイル基、もしくはスルファモイル基であり、
Ｙ^２は、水素原子、または置換基を有しても良い、アルケニル基、アルキル基、アルキルオキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基アシルオキシ基、もしくはアミノ基である。
Ｚは、直接結合又は−ＣＯ−基、
Ｙ^３は、置換基を有しても良いカルバゾール基を含む１価の有機基、Ｐｈ−Ｓ−Ｐｈ−基（Ｐｈは、置換基を有しても良い、フェニル基又はフェニレン基を示す）等であることが好ましい。 (Oxime ester-based photopolymerization initiator represented by the general formula (3))
General formula (3)

In the general formula (3)
Y ¹ may have a hydrogen atom or 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. , Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group.
Y ² may have a hydrogen atom or 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. , Alkyl sulphinyl group, aryl sulphinyl group, alkyl sulfonyl group, aryl sulfonyl group acyloxy group, or amino group.
Z is a direct bond or -CO- group,
Y ³ is a monovalent organic group containing a good carbazole group which may have a substituent, Ph-S-Ph- group (Ph may have a substituent, a phenyl group or represents a phenylene group) Etc. are preferable.

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, which have a plurality of carbon atoms in the structure. -It may have a carbon double bond, and specific examples thereof include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, and a 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 can be mentioned, but the present invention is not limited thereto.

The alkyl group which may have a substituent in 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 Included are linear, branched, monocyclic or condensed polycyclic alkyl groups interrupted by more than one —O—. Specific examples of linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl. 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 linear and branched alkyl groups having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- are -CH ₂ -O-CH ₃ and -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 ( wherein n is 1 from a _{8), -} (CH 2 is _{-CH 2 -CH 2 -O) m -CH} 3 ( wherein m is 5 _{1), - CH 2 -CH (} CH 3) -O-CH 2 - CH ₃ −, −CH ₂ −CH− (OCH ₃ ) _{2, and the} like can be mentioned, but the present invention is not limited thereto.

Specific examples of monocyclic or condensed polycyclic alkyl groups having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include, but are limited to: It is not something that will be done.

The ^{alkyloxy group which may have a substituent in Y 1} is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Included are linear, branched, monocyclic or condensed polycyclic alkyloxy groups optionally interrupted by one or more —O—s. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy groups having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group and 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, boronyloxy group , 4-Decilcyclohexyloxy group and the like can be mentioned, but the present invention is not limited thereto. Specific examples of linear and branched alkyloxy groups having 2 to 18 carbon atoms and optionally interrupted by one or more -O- are -O-CH _2- O-CH ₃ , and. -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 (where n is 1 to 8), -O- (CH _2- CH ₂ -CH ₂ -O) _m- CH ₃ (where m is 1 to 5), -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. Not limited.

Examples of the aryl group which may have a substituent in Y ¹ include a monocyclic or fused polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. Group, 1-anthrill group, 9-anthrill group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthril group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphthyl Group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-kisilyl group, 2,5-kissyl group, mesityl group, p. -Cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, Examples thereof include, but are not limited to, an o-mercaptophenyl group, a p-cyanophenyl group, an m-nitrophenyl group, and an m-azidophenyl group.

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

Examples of the heterocyclic group which may have a substituent in 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, phenoxatyynyl group, 2H-pyrrylyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridadinyl group, indridinyl group, isoindrill group, 3H-indrill group , 2-Indolyl group, 3-Indrill group, 1H-Indazolyl group, Prinyl group, 4H-Kinolidinyl group, Isoquinolyl group, Kinolyl group, Phthalazinyl group, Naftyridinyl group, Kinoxanyryl group, Kinazolinyl group, Synnolinyl group, Pteridinyl group, 4aH- Carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbazolyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group. , Isoxazolyl group, Frazanyl group, 3-Phenixazinyl group, Isochromanyl group, Chromanyl group, Pyrrolidinyl group, Pyrrolinyl group, Imidazolidinyl group, Imidazolinyl group, Pyrazolydinyl group, Pyrazolinyl group, Piperidyl group, Piperazinyl group, Indolinyl group, Isoindrinyl group. , Morphorinyl group, thioxanthril group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxatyynyl group, 3-cummarinyl group and the like, but are limited thereto. It's not a thing.

Examples of the ^{heterocyclic oxy group which may have a substituent in 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 thereof include 2-furanyloxy group, 2-thienyloxy group, 2-indrilloxy group, 3-indrilloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group and 2-carbazoli. Examples thereof include, but are not limited to, a luoxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group.

A good alkylsulfanyl group optionally having a substituent in Y ^1, number 1 to 18 linear, branched, monocyclic or fused polycyclic alkylthio group, and 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.

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

A good alkylsulfinyl group optionally having a substituent in Y ^1, preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specific examples, methylsulfinyl group, ethylsulfinyl group, propyl sulfinyl group, isopropyl sulfinyl group, Butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, etc. However, it is not limited to these.

A good arylsulfinyl group optionally having a substituent in Y ^1, preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specific examples, phenylsulfinyl group, a 1-naphthylsulfinyl group, a 2-naphthylsulfinyl group, 2-Chlorophenyl sulfinyl group, 2-methylphenyl sulfinyl group, 2-methyloxyphenyl sulfinyl group, 2-butyloxyphenyl sulfinyl group, 3-chlorophenyl sulfinyl group, 3-trifluoromethylphenyl sulfinyl group, 3-cyanophenyl sulfinyl group , 3-Nitrophenyl Sulfinyl Group, 4-Fluorophenyl Sulfinyl Group, 4-Cyanophenyl Sulfinyl Group, 4-Methyloxyphenyl Sulfinyl Group, 4-Methyl Sulfanylphenyl Sulfinyl Group, 4-Phenyl Sulfanylphenyl Sulfinyl Group, 4-Dimethylamino Examples thereof include, but are not limited to, a phenylsulfinyl group.

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

The arylsulfonyl group which may have a substituent in Y ^1, preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples include a phenylsulfonyl group, a 1-naphthylsulfonyl group, 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-Phenylsulfanylphenylsulfonyl Group, 4-Dimethylamino Examples thereof include, but are not limited to, phenylsulfonyl groups.

Examples of the acyl group which may have a substituent in Y ¹ include a hydrogen atom, a carbonyl group in which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, and a carbon number of carbon atoms. A carbonyl group substituted with an alkyloxy group of 2 to 20, a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, and a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms are present. Examples thereof include a carbonyl group in 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, and specific examples thereof 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, crotonoyle Group, isoclotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyl Oxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoil group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitro Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrryloxycarbonyl group, 3-fluoroyl Groups, 2-tenoyl groups, nicotinoyle groups, isonicotinoyl groups and the like can be mentioned, but are not limited thereto.

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 thereof include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, and a pentanoyloxy group. Examples thereof include a group, a trifluoromethylcarbonyloxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, a 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, a dibenzylamino group and the like. Can be mentioned.

Here, as the alkylamino group, a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group and a 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 Examples thereof include an amino group, a cyclopropylamino group, a cyclobutylamino group, a cyclopentylamino group, a cyclohexylamino group, a cycloheptylamino group, a cyclooctylamino group, a cyclododecylamino group, a 1-adamantamino group, a 2-adamantamino group and the like. , Not limited to these.

Examples of the dialkylamino group include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group and 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 thereof include, but are not limited to, piperadino groups.

Examples of the arylamino group include anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group and 4-. Examples thereof include, but are not limited to, a biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, and a p-terphenylamino group.

Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditrilamino 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 and N. Examples thereof include, but are not limited to, an ethylanilino group and an N-methyl-1-naphthylamino group.

Examples of the phosphinoyl group which may have a substituent in Y ¹ include a phosphinoyl group having 2 to 50 carbon atoms, and specific examples thereof include a dimethylphosphinoyl group, a diethylphosphinoyl group, and a dipropylphosphinoyl. Examples include, but are limited to, a group, a diphenylphosphinoyl group, a dimethoxyphosphinoyl group, a diethoxyphosphinoyl group, a dibenzoylphosphinoyl group, a bis (2,4,6-trimethylphenyl) phosphinoyl group and the like. It is not something that is done.

Examples of the carbamoyl group which may have a substituent in Y ¹ include a carbamoyl group 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-cyanophenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl Examples thereof include, but are not limited to, -N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

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-alkyl sulfamoyl group, and an N-aryl sulfamoyl. Examples include groups, N, N-dialkylsulfamoyl groups, N, N-diarylsulfamoyl groups, N-alkyl-N-arylsulfamooil groups and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsul. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenyl sulfamoyl group, N-2-chlorophenyl sulfamoyl group, N-2-methoxyphenyl sulfamoyl group, N-2-isopropoxyphenyl sulfamoyl group, N-3-chlorophenyl sulfamoyl group, N-3-nitrophenyl sulfamoyl group, N-3-cyanophenyl sulfamoyl group, N-4-methoxyphenyl sulfamoyl group, N-4-cyanophenyl sulfamoyl group, N-4-dimethylamino Phenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl Examples thereof include, but are not limited to, a group, an N, N-dibutylsulfamoyl group, an N, N-diphenylsulfamoyl group and the like.

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, which may have a substituent in ^{Y 2.} Examples of the arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group include the above-mentioned alkenyl group which may have a substituent in R1, an alkyl group which may have a substituent, and a substituent. It has 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. Also good heterocyclic oxy group, alkylsulfanyl group which may have a substituent, arylsulfanyl group which may have a substituent, alkylsulfinyl group which may have a substituent, and may have a substituent. It may have a good arylsulfinyl group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an acyloxy group which may have a substituent, and a substituent. Synonymous with amino group.

Examples of these substituents in Y ¹ and Y ² include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, a phenoxy group and a p-tolyloxy. Aryloxy group such as an aryloxy group, a methoxycarbonyl group, a butoxycarbonyl group, an alkoxycarbonyl group such as a phenoxycarbonyl group, an acyloxy group such as an acetoxy group, a propionyloxy group and a benzoyloxy group, an acetyl group, a benzoyl group, an isobutyryl group and an acryloyl group. , Acyl group such as methacryloyl group, metoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group and p-tolylsulfanyl group, methylamino group, cyclohexylamino group and the like. Dialkylamino groups such as alkylamino group, dimethylamino group, diethylamino group, morpholino group, piperidino group, arylamino group such as phenylamino group and p-tolylamino group, methyl group, ethyl group, tert-butyl group, dodecyl group, Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group and other alkyl groups, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl In addition to aryl groups such as groups, furyl groups, heterocyclic groups such as thienyl groups, hydroxy groups, carboxy groups, formyl groups, mercapto groups, sulfo groups, mesyl groups, p-toluenesulfonyl groups, amino groups, nitro groups, Examples thereof include a cyano group, a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumyl group, a dimethylsulfoniumyl group, and a triphenylphenacylphosphoniumyl group.
Further, one or more 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-based photopolymerization initiator represented by the following general formula (4) or (5) is excellent in sensitivity and is preferable.

[Oxime ester-based photopolymerization initiator represented by the general formula (4)]
General formula (4)

Formula (4) has the general formula (3) Z is -CO- in groups, ^{Y 3} corresponds to the case of Ph-S-Ph- ^group, Y 4 to Y ⁶ is a hydrogen atom, or a substituent An alkyl group or an aryl group which may have an alkyl group or an aryl group is preferable.

Further, Y ¹ is preferably an aryl group which may have a substituent, Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and Y ^{4 to Y 6} is preferably a hydrogen atom. ..

The alkyl group which may have a substituent or the aryl group which may have a substituent in ^{Y 4 to Y 6} is synonymous with the alkyl group or the aryl group in ^{Y 1} and Y ^2.

Examples of the substituent of an optionally substituted alkyl group or an optionally substituted aryl group, the same meanings as substituent in Y ¹ and Y ^2.

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

Specific examples of the oxime ester-based 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-based photopolymerization initiator represented by the 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 containing 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 may have a substituent. A good aryl group is preferably an alkyl group having 1 to 20 carbon atoms which may have a hydrogen atom or a substituent as ^{Y 7 to Y 14, or an aryl group which may have a substituent.}

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

"Oxime ester-based photopolymerization initiator represented by the general formula (5a)"
General formula (5a)

Formula (5a) is, Z is a direct bond in general formula (3), Y ³ corresponds to the case of the monovalent organic group containing a good carbazole group which may have a substituent, in the formula (5) Y ^{7 to Y 10} and Y ^{12 to Y 13} are hydrogen atoms.
Further, Y ¹¹ is ^{preferably a Y 15-} CO- group or a nitro group. Y ¹⁵ is ^{synonymous with the substituents 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 metoxalyl group, which may further have a substituent. More preferably, it is a benzoyl group or a nitro group which may have a substituent. As 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 is preferable.

Further, as the substituent in the benzoyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms or an alkyloxy group is preferable. Further, as the alkyl group, a methyl group and an ethyl group are preferable, 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 fused polycyclic alkyl group is preferable, if a carbon number of 2 in the Y ¹ 18 by linear interrupted by one or more -O-, branched, monocyclic or fused polycyclic Synonymous with alkyloxy group.

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

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

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

General formula (5b)

Formula (5b) is, Z in the general formula (3) is -CO- group, Y ³ corresponds to the case of the monovalent organic group containing a good carbazole group which may have a substituent group, the keto form carbazole group It is an oxime ester-based photopolymerization initiator having the above.
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. It is preferably a good aryl group.
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 metoxalyl group is preferable, and a benzoyl group is more preferable.

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

Commercially available products of these oxime ester compounds (D1) are 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE OXE-01) from BASF. ), Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02) is commercially available. In addition, the oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-02998, etc. It is also possible to use an ester-based 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. If it is less than 2 parts by weight, the adhesion of the formed pattern to the substrate may be deteriorated, and if it exceeds 50 parts by weight, a problem may occur in developability or a decrease in brightness after heat treatment at 230 ° C. may occur.
(Acetophenone compound (D2))
An acetophenone-based compound (D2) can be used as the photopolymerization initiator of the photosensitive coloring composition for a color filter of the present invention.
Examples of the acetophenone compound include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-. On, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) -butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like can be mentioned.

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, more preferably 2 to 30 parts by weight from the viewpoint of photocurability and developability, with respect to 100 parts by weight of the colorant. .. If it is less than 1 part by weight, the cross-sectional shape of the formed pattern is deteriorated, and if it exceeds 50 parts by weight, a problem may occur in developability or a decrease in brightness after heat treatment at 230 ° C. may occur.

Further, it is preferable to use the acetophenone compound (D2) and the oxime ester compound (D1) in combination.

(Other photopolymerization initiators)
Other photopolymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl 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) -Il) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4- Triazine compounds such as trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio). )-, 2- (O-benzoyloxime)], or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine and other oxime esters. Compounds; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone and the like. A quinone-based compound; a borate-based compound; a carbazole-based compound; an imidazole-based compound; or a titanosen-based compound or the like is used.
These photopolymerization initiators can be used alone or in admixture of two or more at any ratio as required.

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

<Sensitizer (F)>
The coloring 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 is derived from its skeleton and exhibits absorption over a wide range of 300 to 400 nm, whereby the reaction of the photopolymerization initiator can be enhanced.

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 coloring composition, from the viewpoint of photocurability and developability. It is more preferable that the amount is 3 to 50 parts by weight.

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

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

(Other sensitizers)
Other sensitizers that can be used in combination include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, or 3,3', 4 , 4'-Tetra (t-butylperoxycarbonyl) benzophenone compounds such as benzophenone, chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-represented by benzyl, camphorquinone, etc. Polymethine dyes such as diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoll derivatives, etc. Derivatives, azine derivatives, thiadine derivatives, oxazine derivatives, indolin derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives , Tetraazaporphyrazine derivative, Tetraquinoxalyloporphyrazine derivative, Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anulene derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropyrane derivative, Metal allene complex , Organic ruthenium complex, or Michler ketone derivative, biimidazole derivative, α-acyloxyester, acylphosphine oxide, methylphenylglycilate, benzyl, 9,10-phenanslenquinone, camphorquinone, ethylanthraquinone, 4, Examples thereof include 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 admixture of two or more at any ratio, if necessary.

More specifically, Okawara Nobu et al., "Dye Handbook" (1986, Kodansha), Okawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " Examples thereof include, but are not limited to, the sensitizer described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

<Antioxidant (G)>
The photosensitive coloring composition for a color filter of the present invention can contain an antioxidant (G). The antioxidant is used to prevent the photopolymerization initiator and thermosetting compound contained in the photosensitive coloring composition for color filters from oxidizing and yellowing due to the thermal process during thermal curing or ITO annealing. The transmittance can be increased. In particular, when the concentration of the colorant in the photosensitive coloring composition is high, the amount of the cross-linking component of the coating film is small, so that the yellowing of the thermal process is strong in order to take measures such as using a highly sensitive cross-linking component and increasing the amount of the photopolymerization initiator. The phenomenon is seen.
Therefore, by containing an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and obtain a high transmittance of the coating film.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorption function, a radical capture function, or a peroxide decomposition function, and specifically, the antioxidant is a hindered phenol-based or a hindered amine-based compound. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulcylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Further, the antioxidant used in the present invention preferably does not contain a halogen atom.

Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the preferred ones are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants. Agents are mentioned.

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), and the like. 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-t-butyl-5-methylphenol), 2,2'-thio- Bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) )-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-hydro) Phenol) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

Examples of the hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and 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-piperidyl) imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazin-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) -4-hydroxy-2,2,6,6-polycondensate with tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine and the like. In addition, oligomer-type and polymer-type compounds having a hindered amine structure can also be used.

Phenyl antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecyl. Phenylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, 4,4'isopropyridendiphenol alkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris (2) , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonyl) Phenyl) 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) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis (4-t-butylphenyl) Phosphite, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2, 4-Ditert-butyl-6-methylphenyl) and the like. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.

Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 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, an oligomer-type compound and a polymer-type compound 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- Examples thereof include hydroxy-4-methoxy-5 sulfobenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.

Examples of the triazine-based 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 salicylic acid ester-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate. In addition, oligomer-type and polymer-type compounds having a sulcylic acid ester structure can also be used.

These antioxidants can be used alone or in admixture 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 based on 100% by mass of the solid content of the coloring composition because the spectral characteristics and the sensitivity are good.

<Organic solvent (E)>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated into the coloring agent carrier, and the filter segment is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent (E) is contained to facilitate the formation. The organic solvent is selected in consideration of the solubility of each component of the coloring composition and the safety in addition to the good coatability of the coloring composition.

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, and 1,4-dioxane. , 2-Heptanone, 2-Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-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 Monotershary 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 Diethyl 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 Diethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethylate , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl Cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like can be mentioned.
These solvents can be used alone or in admixture of two or more at any ratio, if necessary.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl have good dispersibility, permeability, and coatability of the coloring composition. It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

Further, since the organic solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness, it should be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant. Is preferable.

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

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The binding 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 polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are repeatedly bonded alternately. Didimethylpolysiloxane 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 to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalline sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as an auxiliary to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphoric acid ester, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazolin, and fluorocarbon and silicone-based surfactants.

(Curing agent, curing accelerator)
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. As the curing agent, a phenol-based resin, an amine-based compound, an acid anhydride, an active ester, a carboxylic acid-based compound, a sulfonic acid-based compound, and the like are effective, but the curing agent is not particularly limited thereto, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (eg, 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 derivative bicyclic amidin compounds and salts thereof (eg, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl). -4-Methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- (2-cyanoethyl) -2-ethyl-4-methyl imidazole, etc.), phosphorus compounds (eg, tri) Phenylphosphin, etc.), guanamine compounds (eg, melamine, guanamine, acetguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2, etc.) 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 be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting resin.

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

(Storage stabilizer)
Examples of the storage stabilizer include organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphite. 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)
Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and 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-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as 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.

(Polyfunctional thiol)
The coloring composition of the present invention may contain a compound having two or more thiol (SH) groups as a polyfunctional thiol.
By using a polyfunctional thiol together with a photopolymerization initiator, a chain transfer agent acts as a chain transfer agent in the radical polymerization process after light irradiation, and a chile radical that is less susceptible to polymerization inhibition by oxygen is generated, so that the obtained coloring composition has high sensitivity. It becomes. In particular, polyfunctional aliphatic thiols in which the SH group is bonded to an aliphatic group such as methylene or ethylene group are preferable. Examples of the polyfunctional thiol include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio. Nate, Trimethylol Propanetristhioglycolate, Trimethylol Prothanitristhiopropionate, Trimethylol Propantris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Tetrakissthiopropionate, Trimercaptopropionic Acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s- Examples thereof include triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropanetristhiopropionate, and pentaerythritol tetrakisthiopropionate.

These polyfunctional thiols can be used alone or in admixture of two or more.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, more preferably 1.0 to 50.0 parts by mass with respect to 100 parts by mass of the colorant (A). If the content of the polyfunctional thiol is less than 0.05 parts by mass, the effect of the chain transfer agent is small, and if it is more than 100 parts by mass, the polymerization initiation function is not improved and the developability, adhesion, etc. are insufficient. ..

<Manufacturing method of coloring composition>
In the coloring composition of the present invention, a colorant (A), a resin-type dispersant (B), a binder resin, an organic solvent (E), a dye derivative and the like, if necessary, are mixed together in a kneader, two roll mills and three. Using various dispersion means such as this roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor, finely disperse to form a colorant dispersion, and if necessary, a binder for 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. Further, in the photosensitive coloring composition containing two or more kinds of colorants, each colorant dispersion may be dispersed in the colorant carrier at the same time, or those dispersed separately in the colorant carrier may be mixed. .. Further, if the colorant is highly soluble, specifically, if it is highly soluble in the solvent used and is in a state where it is not dissolved by stirring and no foreign matter is confirmed, it is necessary to disperse it finely as described above. There is no.

<Removal of coarse particles>
The colored composition of the present invention comprises coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, and coarse particles of 5 μm or more, preferably coarse particles of 0.5 μm or more, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not contain particles having a size of 0.5 μm or more. It is more preferably 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 comprises 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. It can have red, green, and blue filter segments. The filter segment may further include a magenta color filter segment, a cyan color filter segment, and a yellow filter segment.

The base material of the color filter includes glass plates such as soda lime glass, low alkaline borosilicate glass, and non-alkali aluminum borosilicate glass, which have high transmittance for visible light, and polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and the like. Examples thereof include a transparent substrate such as a resin plate or a reflective substrate. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum vapor deposition and the like. Further, 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 display after panelization.

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

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.

The formation of each color filter segment and the black matrix by the photolithography method is performed by the following method. That is, the coloring composition for a color filter prepared as a coloring composition for a solvent-developing type or an alkali-developing type coloring color filter is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating. Apply so that the film thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film.

After that, the filter segment and the black matrix can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion and form a desired pattern. Further, in order to promote the polymerization of the filter segment and the black matrix formed by the development, heating can be applied as needed. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution.
As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid filling) development method and the like can be applied.
In order to increase the UV exposure sensitivity, the coloring composition for a color filter is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. After forming the film, ultraviolet exposure can also be performed.

An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, or the like is formed on the color filter, if necessary.

The color filter is bonded to the facing substrate using a sealing agent, the liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is placed on the outside of the substrate as necessary. By laminating, a liquid crystal display panel is manufactured.

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

Further, the organic EL display device has a color filter and an organic light emitting body, 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 to a light source having a two-wavelength peak, a light source having a three-wavelength peak, and a light source having a large number of peaks in the visible light region, and conventionally known light sources 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.

The method for measuring the weight average molecular weight (Mw) of the resin and the ammonium salt value of the resin having a cationic group in the 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 is converted to polystyrene measured by using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector and using THF as a developing solvent. Weight average molecular weight (Mw).

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

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

<Manufacturing method of resin type dispersant>
<Manufacturing of basic resin type dispersant solution>
(Manufacturing of basic resin type dispersant solution (B-1))
133 parts of propylene glycol monomethyl ether acetate was charged in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110 ° C. while substituting with nitrogen. 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) were charged in the reaction vessel and stirred until uniform. .. After that, 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 mgKOH / g and a heavy average molecular weight of 9000 (Mw) was obtained.
After cooling to room temperature, about 2 g of the resin solution is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate is added so that the non-volatile content becomes 40% by mass to make it basic. A resin-type dispersant solution (B-1) was obtained.

(Manufacturing of basic resin type dispersant (B-2-4))
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 the blending amount (parts by mass) shown in Table 1 are changed. Was synthesized.

<Manufacturing method of acidic resin type dispersant solution>
(Manufacturing of Acid Resin Type Dispersant Solution (B-5))
As the 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 into a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer. 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 was divided into 20 portions and 30 times. It was added every minute and reacted at 80 ° C. for 12 hours, and it was confirmed by solid content measurement that 95% of the reaction occurred. Next, as the second stage synthesis, 30 parts of pyromellitic acid anhydride, 190 parts of propylene glycol monomethyl ether acetate, and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. It was added and reacted at 120 ° C. for 7 hours. It was confirmed by titration that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. In this way, a resin-type dispersant solution having an acid value of 42 mgKOH / g per solid content, 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 is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate is added so that the non-volatile content becomes 40% by mass to make an acidic resin. A mold dispersant solution (B-5) was obtained.

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

＜バインダー樹脂溶液の製造方法＞

<Manufacturing method of binder resin solution>

(Adjustment of acrylic resin solution 1)
370 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C. 18 parts of Milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2'-azobisisobutyronitrile 2.0. The mixture of parts was added dropwise over 2 hours. After the dropping, the reaction was further carried out at 100 ° C. for 3 hours, 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 was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container at 120 ° C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5, the reaction was terminated to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently added and reacted at 120 ° C. for 3.5 hours to prepare 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 non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. An acrylic resin solution 1 which is an active energy ray-curable resin was prepared.

<Manufacturing method of miniaturized pigment>

(Red refined pigment (PR-1))
C. I. Pigment Red 254 (PR254) (BASF's "Irgafore Red B-CF"), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) for 8 hours at 70 ° C. Kneaded. This mixture is put into 2000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 100 parts of a red finely divided pigment (PR-1).

(Red refined pigment (PR-2))
C. I. Pigment Red 177 (PR177) (BASF's "Chromophthalred A2B"), 800 parts of sodium chloride, and 180 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. .. This mixture is put into 4000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 100 parts of a red finely divided pigment (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 in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. This mixture is put into 4000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 100 parts of a red finely divided pigment (PR-3).

(Yellow miniaturized 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.

（化合物（２））

(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. By TOF-MS, the formation of compound (3) and the disappearance of the raw material compound (2) were confirmed. Further, 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 filtered off, washed with methanol and dried to give 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 in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was put into warm water, stirred for 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. 98 parts of a yellow finely divided pigment (PY-1) was obtained.

(Yellow refined pigment (PY-2))
C. I. Pigment Yellow 139 (PY139) (BASF's "Irgafore Yellow 2R-CF"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) for 6 hours at 80 ° C. Kneaded. This mixture was put into 2000 parts of warm water, stirred for 1 hour while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours and 95 parts of yellow. A finely divided pigment (PY-2) was obtained.

(Yellow miniaturized pigment (PY-3))
C. I. Pigment Yellow 139, C.I. I. Pigment Yellow 185 (PY185) (“Paliogen Yellow D1155” manufactured by BASF) was changed to the same procedure as for the production of the yellow colorant (PY-2) to obtain a yellow micronizing pigment (PY-3). rice field.

(Green miniaturized pigment (PG-1))
C. I. Pigment Green 58 (PG58) (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. .. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours. 195 parts of green micronized pigment (PG-1) was obtained.

(Green miniaturized pigment (PG-2))
C. I. Add 500 parts of Pigment Green 7 (PG7) (“Lionol Green YS-07” manufactured by Toyo Color Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) at 120 ° C. Kneaded for 4 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. Then, 490 parts of a green finely divided pigment (PG-2) was obtained.

<Manufacturing method of pigment dispersion>
(Pigment dispersion (DR-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The red pigment dispersion (DR-1) was prepared by filtering with the filter of.

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

As the dye derivative, the one having the structure shown in Table 3 was used.

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

(Pigment dispersion (DG-2))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The red pigment dispersion (DG-2) was prepared by filtering with the filter of.

Green finening treatment 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))
Pigment dispersions (DG-3 to 5) were obtained by the same production method as the pigment dispersion (DG-2) except that the basic resin-type dispersant solution was changed to the composition shown in the table.

<Manufacturing method of photopolymerizable monomer>
(Photopolymerizable monomer (C2-1))
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix M-400 (manufactured by Toagosei Co., Ltd.)) 623 g and hexamethylene diisocyanate 44 g are charged in a 5-port reaction vessel having a content of 1 liter, and at 60 ° C. The reaction was carried out for 8 hours to obtain a product containing polyfunctional urethane acrylate (1). The proportion of the polyfunctional urethane acrylate (1) in the product was 45% by weight, and the photopolymerizable monomer (C2-1) was obtained in which the balance was occupied by another photopolymerizable monomer.
In addition, it was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

(Photopolymerizable monomer (C2-2))
600 g of trimethylolpropane hexamethylene diisocyanate adduct (Coronate HL (manufactured by Tosoh Corporation)) and 950 g of pentaerythritol triacrylate were charged in a 5-port reaction vessel having a content of 1 liter, and reacted at 60 ° C. for 8 hours. A product containing functional urethane acrylate (2) was obtained. The proportion of the polyfunctional urethane acrylate (2) in the product was 80% by weight, and the photopolymerizable monomer (C2-2) was obtained in which the balance was occupied by another photopolymerizable monomer.
In addition, it was confirmed by IR analysis that the isocyanate group was not present in the reaction product.

<Manufacturing method of 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 parts Department ("Aronix M309" manufactured by Toagosei Co., Ltd.)
Photopolymerization Initiator (D1): 1.0 part (BASF "OXE-02")
Solvent: 35.2 parts (Propylene glycol monomethyl ether acetate (PGMAC))

[Examples 2 to 102, Comparative Examples 1 to 9]
(Photosensitive coloring compositions (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 are changed to the types shown in Tables 8 to 13 and the blending amount (part by weight). Except for the above, the photosensitive red coloring composition (RR-2 to 111) was 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 Department ("Aronix M309" manufactured by Toagosei Co., Ltd.)
Photopolymerization Initiator (D1): 1.0 part (BASF "OXE-02")
Solvent: 35.2 parts (Propylene glycol monomethyl ether acetate (PGMAC))

[Examples 104 to 168, Comparative Examples 10 to 16]
(Photosensitive coloring compositions (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 shown in Tables 14 to 17 and the blending amount (part by weight). Photosensitive green coloring compositions (RG-2 to 73) were prepared in the same manner as the photosensitive green coloring composition (RG-1) except for the above.

・Ｄ１−３：下記化学式（５ｂ−２）の構造の化合物

化学式（５ｂ−２）

（アセトフェノン系化合物（Ｄ２））
・Ｄ２−１（ＢＡＳＦ社製「ＩＲＧＡＣＵＲＥ ３６９」
・Ｄ２−２（ＢＡＳＦ社製「ＩＲＧＡＣＵＲＥ ９０７」
（その他の光重合開始剤）
・ｄ−１（アシルフォスフィンオキサイド系化合物、ＢＡＳＦ社製「ＩＲＧＡＣＵＲＥ ８１９」）
＜増感剤＞
（チオキサントン系化合物（Ｆ１））
・Ｆ１−１（日本化薬社製「ＫＡＹＡＣＵＲＥ ＤＥＴＸ−Ｓ」）
（その他の増感剤）
・ｆ−１（ベンゾフェノン系化合物、保土谷化学製「ＥＡＢ−Ｆ」）
（酸化防止剤（Ｇ））
・Ｇ−１（ＢＡＳＦ社製「ＩＲＧＡＮＯＸ １０１０」）
・Ｇ−２（ＡＤＥＫＡ社製「アデカスタブＡＯ４１２−Ｓ」） The abbreviations in Tables 8 to 17 are described below.
<Photopolymerizable monophotomer>
(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)-(OC 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 ("Sun Ester TMP" manufactured by Sanshin Chemical Industry Co., Ltd.)
(Chemical formula 9): (CH ₂ = C (-CH ₃ ) -C (= O) -O-CH ₂ ) _3- CCH ₂ CH ₃
(Photopolymerizable monomer (C2))
・ C2-3 (“UA-1100H” manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
・ C2-4 (“KUA-15N” manufactured by KSM)
(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: Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime)
(BASF's "IRGACURE OXE 02")
D1-2: A compound having the structure of the following chemical formula (5b-1)

Chemical formula (5b-1)

D1-3: A compound having the structure of the following chemical formula (5b-2)

Chemical formula (5b-2)

(Acetophenone compound (D2))
・ D2-1 (BASF's "IRGACURE 369"
・ D2-2 (BASF's "IRGACURE 907"
(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 compound, "EAB-F" manufactured by Hodogaya Chemical Co., Ltd.)
(Antioxidant (G))
・ G-1 (BASF's "IRGANOX 1010")
・ G-2 ("ADEKA STAB AO421-S" manufactured by ADEKA)

<Evaluation of photosensitive coloring composition for color filters>
Using the obtained photosensitive coloring composition, the 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. In this specification, Examples 1 to 11, 15 to 30, 33 to 37, 42 to 48, 53, 59, 68, 71, 73, 79, 81, 82, 86, 87, 90, 92 to 96, 101, 103 to 111, 114, 115, 117 to 121, 124, 125, 128 to 132, 134, 135, 140, 148, 150, 152, 156, 158, 166, 167 are reference examples.

[Development speed evaluation]
A substrate obtained by applying the photosensitive coloring composition on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at a rotation speed at which the film thickness after vacuum drying becomes 3 μm is dried at 70 ° C. for 20 minutes. Then, it was spray-developed with an aqueous sodium carbonate solution at 23 ° C., and the developability was evaluated in three stages. The alkaline developer is from 0.15% by weight of sodium carbonate, 0.05% by weight of sodium hydrogen carbonate, 0.1% by weight of anionic surfactant ("Perex NBL" manufactured by Kao Co., Ltd.) and 99.7% by weight of water. Was used.
The developability evaluation was determined according to the following criteria.
Note that ⊚, ◯, and Δ are practical levels, and × is a level unsuitable for practical use.

⊚: Those that can be completely removed within 40 seconds ○: Those that exceed 40 seconds but can be completely removed within 60 seconds △: Those that exceed 60 seconds but can be completely removed within 80 seconds ×: Those that exceed 80 seconds Things that cannot be completely removed

[Pattern peeling evaluation]
The photosensitive coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm using a spin coater, and dried under reduced pressure to obtain a coating film having a thickness of 3.0 μm. Then, using an ultrahigh pressure mercury lamp, ultraviolet rays were exposed through a photomask having a 100 μm width (pitch 200 μm) stripe pattern. Then, this substrate was developed by a shower developing method using a 00.2 wt% sodium carbonate aqueous solution at 23 ° C. as a developing solution at a developing solution pressure of 0.1 mPa, and heated in a clean oven at 230 ° C. for 20 minutes. The spray development was performed for the coating film of each photosensitive composition in the shortest time during which a pattern could be formed without any development residue, and this was set as the appropriate development time. The pattern in the formed 100 μm photomask portion was observed and evaluated using an optical microscope. The evaluation ranks are as follows.

○: Good without peeling or chipping: Good level △: No peeling but partial chipping occurs: Inferior to ○ but practical level ×: Many peeling and chipping occur: 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 the evaluation of pattern peeling was observed and evaluated using an electron microscope. This substrate was used as the initial development substrate. The pattern cross section has a good forward taper. The evaluation ranks are as follows.

⊚: Forward taper shape with gentle cross section ○: Forward taper shape with cross section ×: Reverse taper shape with reverse cross section

<2> Development resistance evaluation substrate Subsequently, a pattern was produced by the same method as the above-mentioned pattern peeling evaluation pattern, but the development time was such that the coating film with each photosensitive composition formed a pattern without any development residue. It was developed for another 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 evaluation ranks are as follows.

⊚: Forward taper shape with gentle cross section ○: Forward taper shape with cross section ×: Reverse taper shape with reverse cross section

[Chemical resistance evaluation]
<NMP resistance test evaluation 1>
For the stripe pattern formed for the pattern peeling evaluation, the chromaticity ([L * (1), a * (1), b * (1)]) at the C light source is measured by a microspectroscopy (manufactured by Olympus Optical Co., Ltd.). It was measured using "OSP-SP100"). Further, the substrate on which the stripe pattern is formed is immersed in NMP for 15 minutes, washed with water, dried, and then chromaticity with a C light source ([L * (2), a * (2), b * (2)]). Was measured, and the color difference ΔE * ab was obtained by the following 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 )

⊚: 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 substrate on which the stripe pattern formed for the pattern peeling evaluation was formed was immersed in NMP for 15 minutes, washed with water and dried, and then the appearance of the green pixels was observed by the following method.
The surface of 50 pixels was observed using a metallurgical microscope "BX60" (manufactured by Olympus System Co., Ltd.) with 25 μm × 100 μm as one pixel. The magnification was set to 500 times, and the number of pixels in which cracks were generated by reflection was counted. The evaluation was made in the following four stages.

⊚: 50 pixels No cracks ○: Number of cracks 1 or more and less than 10 Δ: Number of cracks 10 or more and less than 30 ×: Number of cracks 30 or more

<Heat resistance evaluation>
The photosensitive coloring composition is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater at a rotation speed at which the film thickness after vacuum drying becomes 3 μm, and then dried at 70 ° C. for 20 minutes. Then, the coating film substrate was prepared by heating at 230 ° C. for 20 minutes and allowing to cool. The chromaticity of the obtained coating film at the C light source ([L * (1), a * (1), b * (1)]) was measured with a microspectroscopy (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Measured using. After that, as a heat resistance test, the mixture was heated at 230 ° C. for 3 hours, the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured, and the following formula was used. , Color difference ΔEab * was obtained and evaluated in the following four stages.

ΔE * ab = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
⊚: 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 to 25, a photosensitive coloring composition containing at least one photopolymerizable monomer (C1) in which the photopolymerizable monomer is selected from the general formulas (1) and (2). By using the colorant, 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 a color filter. The pattern cross-sectional shape was also good.

Further, when the content of the colorant is 45% by weight or more and the glass transition temperature (Tg) of the resin type dispersant (B) is in the range of 20 to 100 ° C., the pattern is peeled off and the chemical resistance is good. The 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 pattern peeling was improved by using the oxime ester compound (D1), and the development resistance of the pattern cross-sectional shape was improved when the acetophenone compound (D2) was used in combination. Further, when the content of the colorant is high, the pattern cross-sectional shape is generally deteriorated, but by containing the thioxanthone compound (D) as a sensitizer, the development resistance of the pattern cross-sectional shape is improved. I was able to improve it.

In addition, when the content of the colorant was high, the heat resistance was improved by using an antioxidant.

From the above results, the photosensitive coloring composition of the present application makes it possible to obtain a colored film having an excellent pattern shape and good chemical resistance even when the content of the coloring agent is high, thereby achieving high color reproducibility. It was possible to form a color filter.
That is, the photosensitive coloring composition of the present invention is required not only for a color liquid crystal display device but also for a thin film and a wide color reproduction range such as a color image pickup device, a quantum dot display device, and an organic EL display device. It can be preferably used.

Claims (7)

A colorant (A) (excluding carbon black), 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 containing
The content of the colorant (A) is 40% by weight or more in 100% by weight of the total solid content of the photosensitive coloring composition for a color filter.
The glass transition temperature (Tg) of the resin-type dispersant (B) is 20 to 100 ° C., and the photopolymerizable monomer (C) is the photopolymerizable monomer (C1 ) of the following general formula (2). ) Is contained in a photosensitive coloring composition for a color filter.
( General formula 2): (CH ₂ = C (-R) -C (= O)-(OR ₁ ) n-O-CH ₂ ) _{3- CCH 2} CH ₃
[In the formula, 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 photopolymerizable monomer (C) further contains a polyfunctional urethane acrylate (C2). The photosensitive coloring composition for a color filter according to claim 1 or 2, wherein the photopolymerization initiator (D) contains an oxime ester compound (D1). The photosensitive coloring composition for a color filter according to any one of claims 1 to 3, wherein the photopolymerization initiator (D) contains an acetophenone-based compound (D2). The photosensitive for a color filter according to any one of claims 1 to 4, further comprising a sensitizer (F) and the sensitizer (F) containing a thioxanthone-based compound (F1). Coloring composition. The photosensitive coloring composition for a color filter according to any one of claims 1 to 5, further comprising an antioxidant (G). 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 6 on a substrate.