JP2009237151A - Coloring curing composition for color filter and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring curing composition for color filter having excellent performance for removing alkaline development and excellent solubility in a developer and capable of forming a cured film having small surface roughness; and to provide the color filter formed by using this composition. <P>SOLUTION: The coloring curing composition for color filter contains (A) a coloring agent, (B) a binder resin, (C) a photopolymeric compound having an ethylene unsaturated bond, (D) a photopolymerization initiator, and (E) a solvent that satisfies the following conditions (i)-(iv): (i) the content of (A) the coloring agent is 30-60 wt.% for the total mass of solids of the coloring curing composition; (ii) acid value of (B) the binder resin is 150-240 mgKOH/g; (iii) weight percentage of the content of the photopolymeric compound having (C) the ethylene unsaturated bond to the content of (B) the binder resin is 0.30-0.50; and (iv) (D) the photopolymerization initiator contains at least either of triazine compound and oxime compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a colored curable composition for a color filter, and a color filter.

  A color filter generally contains a colorant such as an organic pigment or an inorganic pigment, a polyfunctional monomer, a photopolymerization initiator, a binder resin, and other components to form a colored curable composition, which is used as a photolithographic method. It is manufactured by forming a colored pattern by, for example.

  In recent years, the use of color filters in liquid crystal display (LCD) applications has tended to expand not only to monitors but also to televisions (TVs). With this trend of expanding applications, advanced color characteristics such as chromaticity and contrast. Is required. Further, in a large-sized TV, there is a demand for further high-speed coating suitability and improvement of the voltage holding ratio of the color filter itself for improving the image quality of thin layers. Further, in image sensor (solid-state imaging device) applications, high resolution for forming a fine pattern and high color characteristics similar to those for LCDs have been demanded due to the recent demand for higher image quality.

  In response to the above requirements, there is a demand for forming a pattern having an excellent surface shape and an elaborate shape. Accuracy is required in each step such as formation of a colored curable composition layer, exposure processing, and development processing in the manufacturing process of the color filter. For example, in the case where the development removal of the uncured portion of the colored curable composition that has been subjected to the exposure treatment is insufficient, fringes (jagged edges) and surface irregularities are produced in the formed colored resist film. There are problems that the chromaticity and dimensional accuracy of the color filter are lowered and the contrast is remarkably deteriorated.

  In the colored curable composition, high photosensitivity, solubility in an uncured portion of the developer, and chemical resistance of the image portion are important characteristics. Furthermore, there is an increasing demand for higher color filters and higher optical density (OD value), and there is a tendency for the concentration of colored components in the colored curable composition to be higher. However, when the concentration of the coloring component is increased, there are problems with various characteristics such as an insufficient curing of the exposed portion due to an increase in light absorption by the coloring component. Thus, the increase in the concentration of the coloring component and the characteristics of the colored curable composition are in a trade-off relationship.

In response to these problems, a photosensitive composition containing a monomer into which an acidic group has been introduced in order to impart development removability of a colored curable composition in an unexposed area and a binder resin is disclosed ( For example, see Patent Document 1).
However, even if the development removability can be improved by increasing the acid value, the colored curable composition piece of the unexposed part peeled off by development is difficult if the colored curable composition is difficult to dissolve in the developer. Re-deposited on the substrate, and the surface of the cured film after development tends to be uneven.

JP 2004-287232 A

  In view of the above circumstances, the present invention is excellent in alkali development removability and solubility in a developer, and is formed using a colored curable composition for a color filter capable of forming a cured film having a small surface roughness. It is an object to provide an improved color filter.

Specific means for achieving the above object are as follows.
<1> contains (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound having an ethylenically unsaturated bond, (D) a photopolymerization initiator, and (E) a solvent. These are colored curable compositions for color filters that satisfy the following i) to iv).
i) Content of said (A) coloring agent is 30 mass%-60 mass% with respect to the total solid content mass of colored curable composition.
ii) The acid value of the (B) binder resin is 150 mgKOH / g to 240 mgKOH / g.
iii) The mass ratio of the content of the (C) photopolymerizable compound having an ethylenically unsaturated bond to the content of the (B) binder resin is 0.30 to 0.50.
iv) The (D) photopolymerization initiator contains at least one of a triazine compound and an oxime compound.

  <2> The color according to <1>, wherein the total content of the triazine-based compound and the oxime-based compound is 20% by mass or more based on the total solid content mass of the (D) photopolymerization initiator. It is a coloring curable composition for filters.

  <3> The colored curable composition for color filters according to <1> or <2>, wherein the photopolymerizable compound (C) having an ethylenically unsaturated bond contains an acidic group or a hydroxyl group.

  <4> The color curable composition for a color filter according to <3>, wherein the acid value of the (C) photopolymerizable compound having an ethylenically unsaturated bond having an acidic group is 20 mgKOH / g to 90 mgKOH / g. It is a thing.

  <5> The colored curable composition for a color filter according to <3>, wherein the hydroxyl value of the photopolymerizable compound having an ethylenically unsaturated bond (C) having a hydroxyl group is 90 mgKOH / g to 140 mgKOH / g. It is.

  <6> A color filter formed using the colored curable composition for a color filter according to any one of <1> to <5>.

  According to the present invention, a colored curable composition for a color filter, which is excellent in alkali development removability and solubility in a developer, and can form a cured film with small surface roughness, and a color formed using the same A filter can be provided.

<Colored curable composition for color filter>
The colored curable composition for a color filter of the present invention comprises at least (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound having an ethylenically unsaturated bond, and (D) photopolymerization initiation. And (E) a solvent, i) the content of the (A) colorant is 30% by mass to 60% by mass with respect to the total solid mass of the colored curable composition, and ii) The acid value of the (B) binder resin is 150 to 240 mgKOH / g, and iii) the content of the photopolymerizable compound having the (C) ethylenically unsaturated bond with respect to the content of the (B) binder resin. The mass ratio is 0.30 to 0.50, and iv) the (D) photopolymerization initiator contains at least one of a triazine compound and an oxime compound.
The colored curable composition for color filters of the present invention (hereinafter, the colored curable composition for color filters is also simply referred to as “colored curable composition”) has the above-described configuration satisfying the requirements i) to iv). Thus, even if it contains a large amount of colorant, it is excellent in alkali development removability and easily dissolved in the developer. Therefore, even if the colored curable composition piece (solid content) in the unexposed area is peeled and removed by the development treatment, the peeled solid content is dissolved in the developer and hardly remains in the developer. Therefore, it is possible to prevent the solid content from reattaching to the surface of the substrate or the cured film (cured colored curable composition layer; pattern) after development. As a result, it is possible to suppress the occurrence of surface irregularities due to the redeposition of the solid content of the cured film after development, and to form a color filter having a cured film with a small surface roughness (Ra). It is considered a thing.

The surface roughness (Ra) is a center line average roughness (Ra) obtained by measuring an area of 10 μm square using a Nano Scope IIIa (AFM) apparatus manufactured by Digital Instruments.
Hereinafter, the components (A) to (E) of the colored curable composition for a color filter of the present invention will be described.

[(A) Colorant]
The colored curable composition for a color filter of the present invention contains (A) a colorant, and the content of the (A) colorant is 30% by mass to the total solid mass of the colored curable composition. 60% by mass [said requirement i)]. By setting it as the above range, it is possible to meet demands for high concentrations such as for TVs, and when the content exceeds the above range, characteristics such as coating property, sensitivity, and pattern formability cannot be achieved. The content of the colorant is preferably 30% by mass to 50% by mass.
(A) As the colorant, pigments and dyes can be used.

(Pigment)
As the pigment that can be used in the colored curable composition for a color filter of the present invention, various conventionally known inorganic pigments or organic pigments can be used. Moreover, considering that it is preferable that the pigment has a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible and a handling property in consideration of handling properties. Then, it is preferably a pigment having an average primary particle diameter of 0.01 to 0.3 μm, more preferably 0.01 to 0.15 μm. When the particle size is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast.
The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37,
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. Things, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28,
C. I. Pigment Black 1, 7 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37,
C. I. Pigment Black 1, 7

-Finer pigments-
In the present invention, if necessary, a fine and sized organic pigment can be used. The refinement of the pigment is a step of preparing a highly viscous liquid composition together with the pigment, the water-soluble organic solvent, and the water-soluble inorganic salt, and grinding the pigment using the liquid composition.

  Water-soluble organic solvents include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol A monomethyl ether acetate etc. can be mentioned. However, if it is adsorbed to the pigment by using a small amount and does not flow away into the wastewater, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane , Heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Two or more kinds of solvents may be mixed and used as necessary.

  In the present invention, examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.

The amount of the water-soluble inorganic salt used is 1 to 50 times the mass of the pigment, and a larger amount has a grinding effect, but a more preferred amount is 1 to 10 times the mass in terms of productivity, and the water content is 1% or less. It is preferable that
The amount of the water-soluble organic solvent used is in the range of 50% by mass to 300% by mass and preferably in the range of 100% by mass to 200% by mass with respect to the pigment.

  After preparing a liquid composition using each of the above components, the pigment is refined by a wet pulverizer. Here, there are no particular restrictions on the operating conditions of the wet pulverizing apparatus, but in order to effectively proceed the grinding with the pulverizing media, the operating conditions when the apparatus is a kneader are: 200 rpm is preferable, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry pulverization time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. In addition, the water-soluble inorganic salt that is a pulverization medium preferably has a pulverization particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

-Preparation of pigment (color matching)-
The organic pigment as the colorant can be used alone, but can be used in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, and a diketopyrrolopyrrole pigment may be used alone, but at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone pigment A yellow pigment, or a perylene red pigment, an anthraquinone red pigment, or a diketopyrrolopyrrole red pigment may be mixed. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139, or C.I. I. Mixing with Pigment Red 177 is preferred.
The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. If it is less than 100: 5, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 80, the coloring power may decrease. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

As the green pigment, a halogenated phthalocyanine pigment may be used alone, but a mixture of this with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment. May be performed. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180, or C.I. I. Mixing with Pigment Yellow 185 is preferred.
The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 to 450 nm, and the color purity may not be increased. On the other hand, if the ratio exceeds 100: 200, the dominant wavelength tends to be longer and the deviation from the NTSC target hue may become larger. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a phthalocyanine pigment may be used alone, but it may be mixed with a dioxazine purple pigment. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

Moreover, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable.
The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, the dispersion stability may decrease.

(dye)
In the present invention, when a dye is used as the colorant (A), a uniformly curable colored curable composition is obtained.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.
The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

(Pigment dispersion)
In the present invention, when a pigment is used as the colorant (A), it is preferable to prepare the colored curable composition for a color filter of the present invention using a pigment dispersion prepared in advance.
As content of the pigment in a pigment dispersion liquid, 10-60 mass% is preferable with respect to the total solid (mass) of this composition, and 15-50 mass% is more preferable. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

-Dispersant-
The pigment dispersion in the present invention preferably contains at least one dispersant. By containing this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many types of compounds can be used. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants such as 26000, 28000 (manufactured by Nippon Lubrizol Corp.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (by Big Chemie). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

  As content in the pigment dispersion liquid of a dispersing agent, 1-100 mass% is preferable with respect to the mass of the above-mentioned pigment, and 3-70 mass% is more preferable.

-Pigment derivative-
A pigment derivative is added to the pigment dispersion in the present invention as necessary. By adsorbing a pigment derivative having a part having affinity for the dispersant or a polar group to the pigment surface and using this as the adsorption point of the dispersant, the pigment is made into fine particles in the pigment dispersion or colored. It can be dispersed in the curable composition to prevent reaggregation. As a result, this colored curable composition can be preferably used when forming a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included.

  Examples of pigment derivatives include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. For example, JP-A-2005-234478, JP-A-2003-240938, and JP-A-2001-356210 can be used.

  As content in the pigment dispersion liquid of a pigment derivative, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

-Distribution method-
As a method for dispersing the pigment, for example, a bead disperser using a zirconia bead (for example, a disperse mat manufactured by GETZMANN), which is prepared by mixing a pigment and a dispersant and previously dispersing the mixture with a homogenizer or the like, is used. And a fine dispersion method is used.
The dispersion time is preferably about 3 to 6 hours.

[(B) Binder resin]
The colored curable composition for a color filter of the present invention contains a binder resin (hereinafter also referred to as “alkali-soluble resin”).
In the present invention, as the binder resin (B), a resin having an acid value of 150 mgKOH / g to 240 mgKOH / g is used [said requirement ii)]. When the acid value is less than 150 mgKOH / g, the development removability is insufficient, and when it exceeds 240 mgKOH / g, the colored curable composition does not sufficiently dissolve in the developer. (B) It is preferable that the acid value of binder resin is 190 mgKOH / g-220 mgKOH / g.

  (B) The binder resin is a linear organic high molecular polymer having at least one alkali-soluble component in a molecule (preferably a molecule having an acrylic copolymer or styrene copolymer as a main chain). An alkali-soluble resin having an accelerating group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.) and having an acid value of 150 mgKOH / g to 240 mgKOH / g can be appropriately selected. . Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For example, a known radical polymerization method can be applied to the production of the binder resin. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As the linear organic polymer, a polymer having a carboxylic acid in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Preferred examples also include acidic cellulose derivatives having a carboxylic acid, and polymers having a hydroxyl group and an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Among these, in particular, benzyl (meth) acrylate and (meth) acrylic acid or benzyl (meth) acrylate / (meth) acrylic acid and other monomers are set to have an acid value of 150 mgKOH / g to 240 mgKOH / g. Those copolymerized with are preferred.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  As a preferable binder resin in the present invention, in particular, (meth) acrylic acid and another monomer copolymerizable therewith are co-polymerized so that the acid value is 150 mgKOH / g to 240 mgKOH / g. Polymerized copolymers may be mentioned. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. = CR ⁷ R ⁸ , CH ₂ = C (R ⁷ ) (COOR ⁹ ) [wherein R ⁷ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁸ is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ⁹ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. And the like.

These other copolymerizable monomers can be used singly or in combination of two or more.
Other preferred copolymerizable monomers are selected from CH ₂ ═CR ⁷ R ⁸ , CH ₂ ═C (R ⁷ ) (COOR ⁹ ), phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene. At least one kind, and particularly preferably CH ₂ = CR ⁷ R ⁸ and / or CH ₂ = C (R ⁷ ) (COOR ⁹ ).

  The binder resin is (B) the total solid content of the colored curable composition of the binder resin relative to the total solid content mass of the colored curable composition of the photopolymerizable compound having an ethylenically unsaturated bond described later. Although it adjusts suitably so that mass ratio of content with respect to mass may be 0.30-0.50, it contains in a colored curable composition, It is preferable that it is the following range. That is, 1% by mass to 15% by mass is preferable, more preferably 2% by mass to 12% by mass, and particularly preferably 3% by mass to 10% by mass with respect to the total solid content mass of the composition. is there.

[(C) Photopolymerizable compound having an ethylenically unsaturated bond]
The photopolymerizable compound having an ethylenically unsaturated bond constituting the colored curable composition for color filters of the present invention (hereinafter sometimes simply referred to as “photopolymerizable compound”) is at least one addition polymerization. A compound having a possible ethylenically unsaturated group and a boiling point of 100 ° C. or higher at normal pressure is preferable, and a tetrafunctional or higher functional acrylate compound is more preferable.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxy Monofunctional acrylates and methacrylates such as ethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ester Ter, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylol ethane, added with ethylene oxide and propylene oxide and then (meth) acrylated, poly (pentaerythritol or dipentaerythritol) (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in Japanese Patent Publication No. 52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.

Also, urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, Urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a curable composition having a very high photosensitive speed.
As these commercial products, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

In the present invention, from the viewpoint of improving development removability, it is preferable that the (C) photopolymerizable compound has an acid group or a hydroxyl group in the molecule.
(C) Examples of the acid group that the photopolymerizable compound may have in the molecule include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. Among them, a carboxylic acid group is preferable from the viewpoint of improving development removability. preferable. Moreover, the hydroxyl group which (C) a photopolymerizable compound may have in a molecule | numerator does not contain OH group which comprises the said carboxylic acid group.

  Furthermore, the acid value of the photopolymerizable compound having an acid group is preferably 20 mgKOH / g to 90 mgKOH / g, and more preferably 50 mgKOH / g to 90 mgKOH / g. The hydroxyl value of the photopolymerizable compound having a hydroxyl group is preferably 90 mgKOH / g to 140 mgKOH / g, and more preferably 100 mgKOH / g to 130 mgKOH / g.

  Examples of commercially available photopolymerizable compounds having an acid group include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and TO-1382, which is a carboxyl group-containing pentafunctional acrylate. 1385 or the like.

  Examples of commercially available photopolymerizable compounds having a hydroxyl group include M-305, which is a hydroxyl group-containing trifunctional acrylate manufactured by Toa Synthetic Chemical Co., Ltd., and M-403, M-404, which are hydroxyl group-containing pentafunctional acrylates. Is mentioned.

  Both acid group-containing monomer and hydroxyl group-containing monomer are dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and their acryloyl groups are ethylene glycol and propylene glycol residues from the viewpoint of polymerization sensitivity and alkali solubility. A structure via a group is preferred. These oligomer types can also be used.

In the present invention, the mass ratio of the content of the photopolymerizable compound (C) having an ethylenically unsaturated bond to the content of the binder resin (B) is 0.30 to 0.50 [said requirement iii )]].
That is, the content of the photopolymerizable compound having an ethylenically unsaturated bond (C) with respect to the total solid mass of the colored curable composition is “γ”, and the total content of the colored curable composition of the binder resin (B). When the content with respect to the mass of the solid content is “β”, the mass ratio (γ / β; also referred to as “γ / β ratio”) of both needs to be 0.30 to 0.50. When the γ / β ratio is less than 0.30, it is difficult to obtain a sufficient polymerization strength due to an insufficient amount of monomer as a polymerization material. On the other hand, if the γ / β ratio exceeds 0.50, the amount of the binder resin that is an alkali-soluble component decreases, and the solubility in the developer deteriorates.
The γ / β ratio is preferably 0.4 to 0.5.

The (C) photopolymerizable compound in the present invention can be used in combination of two or more, in addition to being used alone.
As described above, the photopolymerizable compound is appropriately adjusted so that the γ / β ratio is 0.30 to 0.50 and is contained in the colored curable composition. Is preferred. That is, 5 to 15 parts by mass is preferable with respect to 100 parts by mass of the total solid content of the composition, and more preferably 8 to 12 parts by mass.

[(D) Photopolymerization initiator]
The photopolymerization initiator (D) of the present invention contains at least one of a triazine compound and an oxime compound [the above requirement iv)]. Hereinafter, a photopolymerization initiator containing at least one of a triazine compound and an oxime compound is also referred to as a “specific photopolymerization initiator”.
If either one of the triazine compound and the oxime compound is not included as a photopolymerization initiator, the curable composition of the colored curable composition by exposure becomes insufficient. The problem that an object is developed is likely to occur. Therefore, the surface of the cured film becomes uneven, and a color filter with a flat surface cannot be obtained.

  In the present invention, the triazine compound is a compound having a triazine structure in the molecular skeleton, and examples thereof include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis ( Trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4 -Bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di ( Trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxy Tyryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- ( Diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3 -Chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenyl Coumarin, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- [o-bromo-pN, N-di ( Etoki Carbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, etc. Benzothiazole compounds / trihalomethyl-s-triazine compounds described in Japanese Patent No. -48516.

  Among the above, the triazine compound is 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, from the viewpoint of polymerization sensitivity. -[O-Bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine is preferred.

  In the present invention, the oxime compound is a compound having a structure represented by —C═N—O— in the molecule. For example, octanedione-O-benzoyloxime, J. Org. C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and oxime ester compounds described in JP-A No. 2000-66385.

  Among the oxime compounds, octanedione-O-benzoyloxime and 1- [9-ethyl-6- (2-methylbenzoyl) -9. H-carbazol-3-yl] -ethane-1-one oxime-O-acetate is preferred.

  In the present invention, in addition to the specific photopolymerization initiator, a photopolymerization initiator can be further contained. For example, halomethyl oxadiazole described in JP-A-57-6096, US Pat. No. 4,318791, Europe Aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as Patent Publication EP-88050A, aromatic ketone compounds such as benzophenones described in US Pat. No. 4,1994,420, Fr— (Thio) xanthone-based or acridine-based compounds described in the specification of 2456741, coumarin-based or biimidazole-based compounds described in JP-A-10-62986, sulfonium organic boron complexes such as JP-A-8-015521, etc. Etc.

  Other photopolymerization initiators include acetophenone, ketal, benzophenone, benzoin, benzoyl, xanthone, active halogen compounds (halomethyloxadiazole, coumarin), acridines, biimidazole An oxime ester type is preferable.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Suitable examples include 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1. be able to.

  Preferred examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Preferable examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, and 4,4′-dichlorobenzophenone. Can do.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the active halogen photopolymerization initiator (oxadiazole type, coumarin type) include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl)- 1,3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1 , 3,4-oxodiazole and the like can be preferably mentioned.

  Preferable examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the biimidazole photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, Preferred examples include 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

  In the present invention, other known ones can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the combination of triallylimidazole dimer / p-aminophenylketone described in U.S. Pat. No. 3,549,367, and the like. Can be mentioned.

Moreover, these other photoinitiators and specific photoinitiators can also be used together. At this time, the total content of the triazine-based compound and the oxime-based compound (total content of the specific photopolymerization initiator) is contained in the colored curable composition from the viewpoint of improving the curability of the colored curable composition. It is preferable that it is 20 mass% or more with respect to solid content mass of all the photoinitiators (namely, said other photoinitiator and specific photoinitiator). More preferably, it is 30 mass% or more.
By setting the total content of the specific photopolymerization initiator in the above range, the colored curable composition can be cured more sufficiently by exposure, and the surface of the cured film is more than necessary even during development processing. Since it becomes difficult to develop, unevenness on the surface of the cured film can be suppressed.

  Here, the “total content of the triazine compound and the oxime compound” means the content of the triazine compound when the specific photopolymerization initiator is composed of only the triazine compound. When a polymerization initiator is comprised only with an oxime type compound, it means content of an oxime type compound. Moreover, when the said specific photoinitiator is comprised with a triazine type compound and an oxime type compound, it means the quantity which totaled both content of the triazine type compound and content of the oxime type compound.

  As content in the colored curable composition of a specific photoinitiator, 0.1 mass%-10.0 mass% are preferable with respect to the total solid content mass of this composition, More preferably, it is 0.4. It is mass%-5.0 mass%. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

-Sensitizing dye-
In the present invention, it is preferable to add a sensitizing dye as necessary. Exposure to a wavelength that can be absorbed by the sensitizing dye promotes radical generation reaction of the polymerization initiator component and polymerization reaction of the polymerizable compound thereby. Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

(Spectral sensitizing dye or dye)
Spectral sensitizing dyes or dyes preferred as sensitizing dyes used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll) Chlorophyllin, center metal-substituted chlorophyll), metal complexes (for example, the following compound), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

(Dye having a maximum absorption wavelength at 350 to 450 nm)
Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  More preferable examples of the sensitizing dye include compounds represented by the following general formulas (XIV) to (XVIII).

In general formula (XIV), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents a basic nucleus of the dye in combination with adjacent A ¹ and an adjacent carbon atom. Represents a non-metallic atomic group to be formed, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. Also good. W represents an oxygen atom or a sulfur atom.
Preferred specific examples [(F-1) to (F-5)] of the compound represented by the general formula (XIV) are shown below.

In General Formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (XIV).
Preferable examples of the compound represented by the general formula (XV) include the following [(F-6) to (F-8)].

In the general formula (XVI), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.
Preferable examples of the compound represented by the general formula (XVI) include the following [(F-9) to (F-11)].

In General Formula (XVII), A ³ and A ⁴ each independently represent —S— or —NR ⁶³ , R ⁶³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and L ⁵ , L ⁶ each independently represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ , A ⁴ and adjacent carbon atoms, and R ⁶¹ and R ⁶² each independently represents a monovalent group. They can be non-metallic atomic groups or bonded to each other to form an aliphatic or aromatic ring.
Preferable examples of the compound represented by the general formula (XVII) include the following [(F-12) to (F-15)].

  In addition, examples of suitable sensitizing dyes used in the present invention include those represented by the following formula (XVIII).

In General Formula (XVIII), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom or a sulfur atom or —N (R ¹ ) —, and Y represents an oxygen atom or — N (R ¹ ) — is represented. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and A and R ¹ , R ² , and R ³ are bonded to each other to form an aliphatic group Or an aromatic ring can be formed.

Here, when R ¹ , R ² , and R ³ represent a monovalent nonmetallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or aryl group.
Next, preferred examples of R ¹ , R ² and R ³ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N-alkylureido group, N, N-dialkylureido group, N-arylureido Group, N, N-diarylureido group, N-alkyl-N-arylureido group, N-alkylureido group, N-arylureido group, N-alkyl-N-alkylureido group, N-alkyl-N-arylureido Group, N, N-dialkyl-N-alkylureido group, N, N-dialkyl-N-arylureido group, N-aryl-N-alkylureido group, N-aryl-N-arylureido group, N, N- Diaryl-N-alkylureido group, N, N-diaryl-N-arylureido group, N- Alkyl-N-aryl-N-alkylureido group, N-alkyl-N-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N- Alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group , Carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group Nyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfina Moyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfato group Famoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphonate Group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group). ), A phosphonooxy group (—OPO ₃ H ₂₎ and its conjugate base group (hereinafter referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (—OPO ₃ ( _{aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), Monoarukiruho Honookishi group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugated base group (hereinafter And cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.

  Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group. , Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl Group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonopheny Group, and a phosphate Hona preparative phenyl group.

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and examples of the heteroaryl ring in the particularly preferred heteroaryl group include Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, flaza , Include phenoxazine and the like, it may be further benzo-fused or may have a substituent.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfide Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonato group, monoaryl phosphono group, aryl phospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ¹ , R ² , or R ³ obtained by combining the above substituents and alkylene groups include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Rubonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl -N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N- Tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, Methyl Phosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p -Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be mentioned.

Specific examples of preferred aryl groups as R ¹ , R ² , or R ³ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. preferable.

Specific examples of preferred substituted aryl groups as R ^{1, R 2,} or R ³ is a substituent on the ring-forming carbon atoms of the aryl group described above, (other than a hydrogen atom) a monovalent non-metallic atomic group What has is used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, Examples include 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

In addition, more preferable examples of R ² and R ³ include a substituted or unsubstituted alkyl group. Also, as more preferred examples of R ¹ include substituted or unsubstituted aryl group. The reason is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical, acid or base of the initiator compound is generated. It is estimated that the efficiency is improved.

Next, A in the general formula (XVIII) will be described. A represents an aromatic ring or a heterocyclic ring which may have a substituent. Specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R ¹ and R ² in the general formula (XVIII). , Or the same as those exemplified in the above description of R ³ .
Among them, preferable A includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and particularly preferable A includes an aryl group having an amino group.

  Next, Y in the formula (XVIII) will be described. Y represents a nonmetallic atomic group necessary for forming a heterocyclic ring in cooperation with the above-described A and adjacent carbon atoms. Examples of such a heterocyclic ring include 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocyclic rings that may have a condensed ring, and preferably 5- or 6-membered heterocyclic rings.

Examples of nitrogen-containing heterocycles include L. G. Brooker et al., Journal of American Chemical Society, J. Am. Chem. Soc., Vol. 73 (1951), p. Any of those known to constitute a basic nucleus in merocyanine dyes described in 5326-5358 and references can be suitably used.
Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, 4,5-di (2-furyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chloro Benzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole 4-methoxybenzo Azole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2 ] Thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [ , 2] thiazole, etc.), thianaphtheno-7,6,4,5-thiazoles (eg 4-methoxythianaphtheno-7,6,4,5-thiazole etc.), oxazoles (eg 4-methyl Oxazole, 5-methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole, 4,5-dimethyl oxazole, 5-phenyl oxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole) 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxyben Zooxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.),

  Naphthoxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (eg, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles ( For example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazoles (for example, naphtho [1,2] selenazole, Naphtho [2,1] selenazole, etc.], thiazolines (for example, thiazoline, 4-methylthiazoline, 4,5-dimethylthiazoline, 4-phenylthiazoline, 4,5-di (2-furyl) thiazoline, 4,5 -Diphenylthiazoline, 4,5-di (p-methoxyphenyl) thi Zoline, etc.), 2-quinolines (for example, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6- Ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), 4-quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, Isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (eg, isoquinoline, etc.), benzimidazoles (eg, 1,3-dimethylbenzimidazole, 1,3-diethylbenzimidazole, 1-ethyl-3) -Phenylbenzimidazole, etc.), 3,3-dialkylin Renins (for example, 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.), 2-pyridines (for example, pyridine, 5-methylpyridine, Etc.), 4-pyridine (for example, pyridine etc.) and the like. Moreover, the substituents of these rings may combine to form a ring.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.
Specific examples include benzodithiols (eg, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (eg, naphtho [1,2] dithiol, naphtho [2,1 Dithiols, etc.), dithiols (for example, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonyldithiols, 4,5-diethoxycarbonyldithiols) 4,5-ditrifluoromethyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyldithiol, etc.).

  Of the examples of the nitrogen-containing or sulfur-containing heterocycle formed by Y in cooperation with the above-mentioned A and the adjacent carbon atom in the general formula (XVIII) described above, the partial structure of the following general formula (XVIII-2) The dye having the structure represented by the formula is particularly preferable because it provides a photosensitive composition having high sensitizing ability and extremely excellent storage stability. The dye having the structure represented by the general formula (XVIII-2) is a compound described in detail in Japanese Patent Application No. 2003-311253 as a novel compound.

In General Formula (XVIII-2), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom, a sulfur atom, or —N (R ¹ ) —. R ¹ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and A and R ¹ , R ⁴ , R ⁵ , and R ⁶ are bonded to each other. An aliphatic or aromatic ring can be formed.
In formula (XVIII-2), A and ^{R 1} are the same as in the general formula (XVIII), ^{R 4} and ^{R 2} in the general formula (XVIII), ^{R 5} is ^{R 3} in the general formula (XVIII) And R ⁶ has the same meaning as R ¹ in formula (XVIII).

  Next, the compound represented by formula (XVIII-3), which is a preferred embodiment of the compound represented by formula (XVIII) used in the present invention, will be described.

In the general formula (XVIII-3), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom or a sulfur atom or —N (R ¹ ) —. R ¹ , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ¹ , R ⁴ and R ⁵ are each aliphatic or aromatic. Can be linked to form a ring. Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the substituent on the Ar skeleton needs to have a sum of Hammett values greater than zero. Here, the sum of the Hammett values is greater than 0 means that the substituent has one substituent, and the Hammett value of the substituent may be greater than 0, and has a plurality of substituents. The sum of Hammett values at may be greater than zero.

In formula (XVIII-3), A and ^{R 1} have the same meanings as in formula (XVIII), ^{R 4} and ^{R 2} in the general formula (XVIII), ^{R 5} is ^{R 3} in the general formula (XVIII) It is synonymous with. Ar represents an aromatic ring or heterocyclic ring having a substituent, and specific examples thereof include an aromatic ring or heterocyclic ring having a substituent among those previously described in the description of A in the general formula (XVIII). The specific example which concerns is mentioned similarly. However, as a substituent that can be introduced into Ar in the general formula (XVIII-3), it is essential that the sum of Hammett values is 0 or more. Examples of such a substituent include a trifluoromethyl group, Examples include a carbonyl group, an ester group, a halogen atom, a nitro group, a cyano group, a sulfoxide group, an amide group, and a carboxyl group. The Hammett values of these substituents are shown below. Trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), carbonyl group (eg, —COHm: 0.36, p: 0.43), ester group (—COOCH ₃ , m: 0 .37, p: 0.45), halogen atom (eg, Cl, m: 0.37, p: 0.23), cyano group (—CN, m: 0.56, p: 0.66), sulfoxide group (e.g. _{-SOCH 3, m: 0.52, p} : 0.45), amide groups (e.g. _{-NHCOCH 3, m: 0.21, p} : 0.00), carboxyl group (-COOH, m: 0. 37, p: 0.45). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is. Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

  Preferred specific examples of the sensitizing dye represented by the general formula (XVIII) according to the present invention [Exemplary Compound (F1) to Illustrative Compound (F56)] are shown below, but the present invention is not limited to these. Absent.

  Among the sensitizing dyes applicable to the present invention, the compound represented by the general formula (XVIII) is preferable from the viewpoint of deep part curability.

  The above sensitizing dye can be subjected to various chemical modifications as follows for the purpose of improving the characteristics of the photosensitive composition of the present invention. For example, by combining a sensitizing dye and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, It is possible to improve the effect of suppressing the unnecessary precipitation of the dye from the crosslinked cured film.

The content of the sensitizing dye is preferably 0.01% by mass to 20% by mass, and more preferably 0.01% by mass to 10% by mass with respect to the total solid mass of the colored curable composition for a color filter of the present invention. It is mass%, More preferably, it is 0.1 mass%-5 mass%.
When the content of the sensitizing dye is within this range, it is highly sensitive to the exposure wavelength of the ultra-high pressure mercury lamp, and it is preferable in terms of development margin and pattern formability as well as deep film curability.

(D) The type of the photopolymerization initiator is appropriately selected according to the use of the coloring pattern described later. For example, for forming a colored pixel of a color filter for use in a liquid crystal display device, a triazine-based, biimidazole-based initiator, etc. Preferably, triazine-based and oxime-based initiators are preferable for forming the black matrix, and oxime-based initiators are preferably used for forming the colored pixels of the solid-state imaging device.
(D) As content in the colored curable composition of a photoinitiator, 0.1 mass%-10.0 mass% are preferable with respect to the total solid content mass of this composition, More preferably, it is 0. 0.5 mass% to 5.0 mass%. When the content of the photopolymerization initiator is within this range, the polymerization reaction can proceed well to form a film with good strength.

[(E) solvent]
In general, the colored curable composition of the present invention can be suitably prepared by using a solvent together with the aforementioned components.
Examples of the solvent used include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and lactic acid. Methyl, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; methyl 3-oxypropionate, ethyl 3-oxypropionate Alkyl 3-esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxy Ethyl propionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol No ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone , Cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene; and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using it independently.

[Other ingredients]
If necessary, the colored curable composition of the present invention includes a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, and the like, as long as the effects of the present invention are not impaired. In addition, various additives such as a filler, a polymer compound other than the alkali-soluble resin, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an anti-aggregation agent can be contained.

(Chain transfer agent)
Examples of the chain transfer agent which can be added to the colored curable composition of the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2 -Mercapto compounds having a heterocyclic ring such as mercaptobenzoxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

(Fluorine organic compounds)
The colored curable composition of the present invention contains a fluorine-based organic compound, thereby improving liquid properties (particularly fluidity) when used as a coating solution, and improving coating thickness uniformity and liquid-saving properties. be able to.
In other words, a colored curable composition containing a fluorine-based organic compound reduces the interfacial tension between the surface to be coated and the coating liquid, improves the wettability to the surface to be coated, and improves the coating property to the surface to be coated. Therefore, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  The fluorine content in the fluorine-based organic compound is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. When the fluorine content is within this range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorinated organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink and Chemicals, Inc.) Manufactured), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).

As the fluorine surfactant which is one of the fluorine-based organic compounds, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used.
Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R-61, R-90 (Dainippon Ink Co., Ltd.), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (Sumitomo 3M Co., Ltd.) Asahi Guard AG 7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102 SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (manufactured by JEMCO).

  In particular, the fluorine-based organic compound is effective in preventing coating unevenness and thickness unevenness when forming a thin coating film using the colored curable composition of the present invention. Furthermore, it is also effective when the colored curable composition of the present invention is applied to slit coating that easily causes liquid breakage.

  The addition amount of the fluorine-based organic compound is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the colored curable composition. is there.

(Thermal polymerization initiator)
It is also effective to contain a thermal polymerization initiator in the colored curable composition of the present invention.
Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds.
Examples of the azo compounds include azobis compounds, and examples of the peroxide compounds include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and peroxide. Examples thereof include oxydicarbonate.

(Thermal polymerization component)
It is also effective to contain a thermal polymerization component in the colored curable composition of the present invention.
An epoxy compound can be used as the thermal polymerization component in order to increase the strength of the coating film formed from the colored curable composition of the present invention.
The epoxy compound is a compound having two or more epoxy rings in the molecule such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound. For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 and the like ( In addition to Tonasei Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (Nagase Kasei Co., Ltd.), Plaxel GL-61, GL-62, G101, G102 (Made by Daicel Chemical) These similar bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UC Corporation) can also be used.

Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 and the like (manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125 and the like (manufactured by Nagase Kasei). Examples of the biphenyl type include 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl.
Furthermore, as the alicyclic epoxy compound, Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Co., Ltd.), Santo Tote ST- 3000, ST-4000, ST-5080, ST-5100, etc. (manufactured by Tohto Kasei Co., Ltd.).
1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resin can also be used.

(Surfactant)
Various surfactants may be added to the colored curable composition of the present invention from the viewpoint of improving coatability. As the surfactant, various nonionic, cationic, and anionic surfactants can be used in addition to the above-mentioned fluorine-based surfactant.
Of these, fluorine-based surfactants having a perfluoroalkyl group and nonionic surfactants are preferred as the nonionic surfactant.

Examples of nonionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Particularly preferred. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene triethyl ether Polyoxyethylene aryl ethers such as benzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, ethylenediamine polyoxyethylene-polyoxypropylene Nonionic surfactants such as thione condensates, which are commercially available from Kao Corporation, Nippon Oil & Fats Co., Ltd., Takemoto Oil & Fat Co., Ltd., ADEKA Co., Ltd., Sanyo Chemical Co., Ltd. Can be used as appropriate.
In addition to these, the above-mentioned dispersants can also be used as the surfactant.

(Other additives)
In addition to the above, various additives can be added to the colored curable composition of the present invention.
Specific examples of the additive include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and aggregation preventing agents such as sodium polyacrylate. Fillers such as glass and alumina; itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, and acid anhydrides added to hydroxyl group-containing polymers And alcohol-soluble nylon, alkali-soluble resins such as phenoxy resin formed from bisphenol A and epichlorohydrin.

Further, when the alkali solubility of the uncured part is promoted and the development removability of the colored curable composition is further improved, the colored curable composition of the present invention is added with an organic carboxylic acid, preferably a molecular weight of 1000. The following low molecular weight organic carboxylic acids are preferably added.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

Further, a thermal polymerization inhibitor may be added to the colored curable composition of the present invention.
Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

  The colored curable composition of the present invention comprises (B) a binder resin, (C) a polymerizable compound, (A) a pigment dispersion prepared by previously containing (A) a colorant, for example, a pigment or a solvent. D) It can be prepared by adding a photopolymerization initiator, (E) a solvent, and, if necessary, an additive such as a surfactant.

The colored curable composition of the present invention has the above-described configuration, that is, (A) a colorant having a specific range of content, (B) a binder resin having a specific range of acid value, and (D) a specific photopolymerization initiator. And (E) a solvent, and a composition in which the γ / β ratio is in a specific range, thereby providing a colored curable composition that is excellent in development removability and is easily dissolved in a developer. Can do.
For this reason, even if this colored curable composition is applied onto a substrate, and the colored pattern obtained by exposure and curing is developed, the unexposed colored curable composition piece peeled and removed by development is regenerated. Surface unevenness due to adhesion can be suppressed. Thus, since the coloring pattern of the smooth surface with small surface roughness (Ra) can be formed if the coloring curable composition of this invention is used, the coloring curable composition of this invention was excellent. It is preferably used for forming a colored region of a color filter for which color characteristics are required, that is, a colored pixel or a black matrix.

<Color filter>
The color filter of the present invention is formed using the colored curable composition for a color filter of the present invention.
By using the colored curable composition for a color filter of the present invention, the colored curable composition for a color filter is cured by exposure to form a cured film, and then a solid content remains on the surface of the cured film when developed. Therefore, the colored curable composition in the unexposed area can be washed away, and the surface roughness (Ra) of the cured film surface after development can be reduced.

A method for producing the color filter of the present invention will be described.
First, the colored curable composition of the present invention is applied on a substrate directly or via another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, and the like. The coating film which consists of an adhesive composition is formed (application | coating process). Then, it exposes with respect to a coating film through a predetermined mask pattern (exposure process). After the exposure, the uncured portion of the coating film is developed and removed with a developer (development process). Through these steps, a colored pattern composed of pixels of each color (three colors or four colors) or a black matrix is formed, and a color filter can be obtained.
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
Since the photosensitive composition of the present invention is excellent in the hydrophilicity of the dried coating film, and is excellent in slit coatability, the effect of the present invention is particularly remarkable when used for the formation of a color filter for a liquid crystal display element having a large area. It can be said.
Hereinafter, each step will be described in detail.

[Coating process]
First, the substrate used in the coating process will be described.
As a substrate used for the color filter of the present invention, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, And a photoelectric conversion element substrate used for a solid-state imaging device or the like, for example, a silicone substrate or a plastic substrate.
On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed is used. In addition, a color filter formed using the colored curable composition of the present invention can be formed to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

In the coating step, the method for applying the colored curable composition of the present invention to the substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter, Slit nozzle coating method) is preferable.
In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. In this case, the discharge amount of the colored curable composition from the slit nozzle is usually 500 microliter / second to 2000 microliter / second, preferably 800 microliter / second to 1500 microliter / second. The speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
Moreover, as solid content of the colored curable composition used at an application | coating process, it is 10 mass%-20 mass% normally, Preferably it is 13 mass%-18 mass%.

When forming the coating film by the coloring curable composition of this invention on a board | substrate, as thickness (after prebaking process) of this coating film, it is generally 0.3 micrometer-5.0 micrometers, Preferably 0.5 micrometer-4 0.0 μm, most desirably 0.5 μm to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking treatment) is preferably in the range of 0.5 μm to 2.0 μm.

In the coating process, usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking.
The vacuum drying condition is that the degree of vacuum is usually about 0.1 torr to 1.0 torr (13.332 Pa to 133.32 Pa), preferably about 0.2 torr to 0.5 torr (26.664 Pa to 66.661 Pa). .
The pre-bake treatment is performed in a temperature range of 50 ° C. to 140 ° C., preferably about 70 ° C. to 110 ° C., using a hot plate, an oven or the like, and can be performed under conditions of 10 seconds to 300 seconds. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. High frequency processing can be used alone.

[Exposure process]
In the exposure step, the coating film made of the colored curable composition formed as described above is exposed through a predetermined mask pattern.
The radiation used for exposure is particularly preferably ultraviolet rays such as g-line, h-line, i-line, and j-line.
When manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine.
Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine.
When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

[Development process]
In the development step, the uncured portion of the coated film after exposure is eluted into the developer, and only the cured portion remains on the substrate.
The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Any developer can be used as long as it dissolves the coating film of the colored curable composition in the uncured part while not dissolving the cured part.
Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

Examples of the organic solvent used for development include the above-described solvents that can be used when preparing the colored curable composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide. , Tetraethylammonium hydroxide, choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001% by mass to 10% by mass, preferably 0 An alkaline aqueous solution dissolved so as to be 0.01 mass% to 1 mass% can be mentioned.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. It is also possible to prevent uneven development by previously moistening the surface to be developed with water or the like before touching the developer. In addition, development can be performed with the substrate inclined.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development process, a rinsing process for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) to complete the curing.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning. You may use the method of using ultrasonic irradiation together.

After rinsing, draining and drying are usually performed at about 200 ° C. to 250 ° C.
In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.

  By repeating the above steps in order for each color according to the desired number of hues, a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed can be produced.

As the application of the colored curable composition of the present invention, the description has mainly focused on the application to the color pattern of the color filter, but also for the formation of a black matrix that isolates the color pattern (pixels) constituting the color filter. Can be applied.
The black matrix on the substrate is a colored curable composition containing a black pigment processed pigment such as carbon black or titanium black, and is subjected to coating, exposure, and development steps. It can be formed by baking.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “%” and “parts” are based on mass.

[Example 1]
-Preparation of pigment dispersion A-1-
The components of the following composition A-1 were mixed using a homogenizer with a rotational speed of 3,000 r. p. m. And mixed for 3 hours to prepare a mixed solution.

(Composition A-1)
-(A) Coloring agent 15 parts Pigment Pigment Red 254 [average particle diameter by SEM observation 25 nm]
Pigment dispersant 3 parts Disperbyk-161 (30% solution manufactured by Big Chemie)
-(B) Binder resin 18.5 parts BzMA / MAA copolymer (= 70/30 [mass ratio])
[Weight average molecular weight (Mw) 5,000, PGMEA solution (solid content 50% by mass)]
・ (E) Solvent Propylene glycol monomethyl ether acetate 66 parts

  BzMA is benzyl methacrylate, MAA is methacrylic acid, and PGMEA is propylene glycol monomethyl ether acetate.

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours in a bead disperser Ultra Apex Mill (manufactured by Kotobuki Kogyo Co., Ltd.) using 0.1 mmφ zirconia beads to obtain a pigment dispersion (A-1). Got.

-Preparation of colored curable composition coating liquid (color resist liquid) F-1-
A component of the following composition F-1 was further added to the pigment dispersion A-1 and mixed by stirring to prepare a colored curable composition coating liquid (color resist liquid) F-1 of Example 1.

(Composition F-1)
-Pigment dispersion A-1 100 parts-Epoxy resin 2 parts EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.)
-(C) Photopolymerizable compound 4.2 parts Dipentaerythritol hexaacrylate (DPHA)
(D) Photopolymerization initiator (a) Octanedione-O-benzoyloxime 1.1 parts (b) Bischlorophenylimidazole 1.7 parts (c) Diethylaminobenzophenone 0.6 parts (d) Mercaptobenzothiazole 0.6 Part ・ Polymerization inhibitor p-methoxyphenol 0.001 part ・ Fluorosurfactant 0.01 part Megafac R08 (manufactured by Dainippon Ink & Chemicals, Inc.)
・ Nonionic surfactant 0.2 parts Tetronic R150 (made by ADEKA)
・ (E) Solvent 130 parts Propylene glycol monomethyl ether acetate (PGMEA)

The colored curable composition of Example 1 was evaluated as follows.
1. Solubility in Developer Using the colored curable composition coating liquid F-1 obtained as described above, a glass substrate having a width of 3 cm and a height of 10 cm was slit-coated by a conventional method to form a coating film. A coating film having a thickness of 2 μm was formed. The coated substrate was immersed in a 1% aqueous solution (25 ° C., 100 cc) of alkaline developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) up to 5 cm and rocked for 20 seconds.
Then, the light absorbency of the developing solution after immersion was measured with UV measuring apparatus U-4100 (made by Hitachi, Ltd.). The measurement wavelength was 510 nm.

When the colored curable composition has good solubility in the developer, the developer is colored, and thus the absorbance of the developer after immersion is high. Therefore, if the absorbance of the developer after immersion exceeds 0.50, almost no peeled pieces of the colored curable composition are observed in the developer, and the solubility is good. Therefore, the solubility in the developer was evaluated as follows.
-Evaluation criteria-
○: Absorbance exceeds 0.5 ×: Absorbance is 0.5 or less The evaluation results are shown in Table 1 below.

2. Film surface roughness after development As in the case of solubility in the developer, the colored curable composition coating solution F-1 is slit-coated on a glass substrate having a width of 10 cm and a height of 10 cm, and the coating film thickness is 2 μm. After the coating film was formed, the entire surface of the coated substrate was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ). The substrate after exposure was immersed in a 1% aqueous solution (25 ° C., 100 cc) of an alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.) and shaken for 20 seconds to obtain a surface roughness (Ra ) Was measured under the following conditions using AFM (Digital Instruments, Nano Scope).
-Measurement conditions-
・ Measurement area: 10μm square ・ Scan Rate: 1Hz

In order to prevent problems such as poor alignment when the color filter formed using the colored curable composition coating liquid F-1 is used to form an LCD panel, the surface roughness Ra of the cured film is: It is preferable that it is 15 nm or less. Therefore, the film surface roughness after development was evaluated as follows.
-Evaluation criteria-
○: Ra is 15 nm or less ×: Ra exceeds 15 nm Evaluation results are shown in Table 1 below.

[Examples 2 to 7 and Comparative Examples 1 to 5]
-Preparation of pigment dispersion-
In the preparation of Pigment Dispersion A-1 in Example 1, the composition of the binder resin and the content (β ′) were changed as shown in Table 1 below. And pigment dispersions A-2 to A-12 of Comparative Examples 1 to 5 were prepared.

-Preparation of colored curable composition coating liquids F-2 to F-12-
In the preparation of the colored curable composition coating liquid F-1 in Example 1, the type and content (γ) of the photopolymerizable compound (monomer), the composition and content of the photopolymerization initiator are shown in Table 1 below. The colored curable composition coating liquids F-2 to F-12 of Examples 2 to 7 and Comparative Examples 1 to 5 were prepared in the same manner except for the above.
The photopolymerization initiator (e) is a triazine compound “4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S—. "Triazine".

-Evaluation-
Using the obtained colored curable composition coating liquids F-2 to F-12, the solubility in a developer and the film surface roughness after development were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1 below.

In Table 1 below, details of BzMA, MAA, DPHA, M-305, and TO-1385 are as follows. The copolymerization ratio of BzMA / MAA is based on mass.
・ BzMA
Benzyl methacrylate MAA
Methacrylic acid / PGMEA
Propylene glycol monomethyl ether acetate DPHA
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.)
・ M-305
Pentaerythritol triacrylate (manufactured by Toagosei Co., Ltd.)
・ TO-1385 (manufactured by Toagosei Co., Ltd.)

In Table 1, the unit of acid value and hydroxyl value is “mgKOH / g”, and the unit of amount (β ′) and amount (γ) is “part by mass”. Numerical values in columns a to e in the initiator column represent contents (parts by mass) in the colored curable composition of the polymerization initiators (a) to (e), and numerical values in a ratio column in the initiator column. These show the ratio (mass%) of the total amount of an oxime type compound (A) and a triazine type compound (E) with respect to all the polymerization initiators used for the colored curable composition.
The unit of pigment concentration is “mass%”. The unit of Ra is “nm”.

  In Table 1, the amount (β ′) is the content of the (B) binder resin (PGMEA solution) in the coloring composition coating solution, and the solid content is 50 mass%. Therefore, the value of “γ / β ratio” in Table 1 is the “value (γ) numerical value” in Table 1 and “the value (β ′) multiplied by 0.5”. Calculated as the divided value.

  As can be seen from Table 1 above, those using the colored curable composition of the present invention (Examples 1 to 7) all have higher solubility in the developer than the comparative examples, and are cured films. The surface roughness (Ra) was found to be small. Those in which the acid value of the binder resin is not included in the range of 150 mgKOH / g to 240 mgKOH / g (Comparative Example 1 and Comparative Example 2), and the γ / β ratio is not in the range of 0.30 to 0.50 ( In Comparative Examples 3 and 4), it was found that the solubility of the colored curable composition in the developer was insufficient. In particular, it was found that the surface roughness of the cured film was further increased when the γ / β ratio was less than 0.30. Further, a photopolymerization initiator that does not use both a triazine compound and an oxime compound (Comparative Example 5) is excellent in the solubility of the colored curable composition in a developer, but the surface roughness of the cured film. It was found that the color curable composition was insufficiently cured.

Claims (6)

It contains (A) a colorant, (B) a binder resin, (C) a photopolymerizable compound having an ethylenically unsaturated bond, (D) a photopolymerization initiator, and (E) a solvent. A colored curable composition for a color filter that satisfies () to (iv).
i) Content of said (A) coloring agent is 30 mass%-60 mass% with respect to the total solid content mass of colored curable composition.
ii) The acid value of the (B) binder resin is 150 mgKOH / g to 240 mgKOH / g.
iii) The mass ratio of the content of the (C) photopolymerizable compound having an ethylenically unsaturated bond to the content of the (B) binder resin is 0.30 to 0.50.
iv) The (D) photopolymerization initiator contains at least one of a triazine compound and an oxime compound.   The colored and cured color filter according to claim 1, wherein a total content of the triazine compound and the oxime compound is 20% by mass or more based on a total solid mass of the photopolymerization initiator (D). Sex composition.   The colored curable composition for a color filter according to claim 1 or 2, wherein the photopolymerizable compound (C) having an ethylenically unsaturated bond contains an acidic group or a hydroxyl group.   The colored curable composition for a color filter according to claim 3, wherein the acid value of the photopolymerizable compound having an acidic group (C) having an ethylenically unsaturated bond is 20 mgKOH / g to 90 mgKOH / g.   The colored curable composition for a color filter according to claim 3, wherein the hydroxyl value of the photopolymerizable compound having a hydroxyl group (C) having an ethylenically unsaturated bond is 90 mgKOH / g to 140 mgKOH / g.   The color filter formed using the coloring curable composition for color filters of any one of Claims 1-5.