JP2009092731A - Colored curable composition, color filter using the same and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable composition which, even with a high pigment concentration, has good developer solubility of an unexposed part and good adhesion to a substrate, produces less development residue, and obtains a pattern of a forward tapered shape. <P>SOLUTION: The colored curable composition has a pigment concentration in a range of 45-60 mass% of a solid content of the composition, and a thermal deformation temperature of the composition after exposure is in a range of 100-200°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is a colored curable composition, and a colored curable composition suitable for producing a color filter used for a liquid crystal display (LCD) or a solid-state imaging device (CCD, CMOS, etc.) obtained by using the colored curable composition. And a color filter having a colored region made of the colored curable composition, and a liquid crystal display device.

  In recent years, the use of color filters in liquid crystal display devices tends to expand not only to mobile and monitor applications but also to televisions. With this trend of application expansion, advanced color characteristics such as chromaticity and contrast are required. Has reached. Similarly, a solid-state imaging device is also required to have high color characteristics.

In response to the demands for the above-mentioned advanced color characteristics, a pigment having a finer particle size and a higher dispersibility is required. In order to enhance the dispersibility of fine pigments, for example, the surface of a phthalocyanine pigment is usually modified with a derivative compound thereof, or a polymer having a polar functional group that is easily adsorbed on the modified surface. A dispersant is used to improve the dispersibility of the fine pigment and stabilize its dispersion. Then, the obtained pigment composition contains an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other components to obtain a colored curable composition, and a color filter is obtained by photolithography using this. Yes.
However, as the pigment becomes finer, a larger amount of dispersant or pigment derivative must be used. For this reason, when forming a pattern by photolithography, alkali solubility becomes poor, or pattern formation by photolithography. However, the load on the color filter manufacturing process is increasing.

  On the other hand, in order to increase color reproducibility, it is indispensable to increase the pigment component of the colored layer to make it darker. For this reason, the colored curable composition for producing a color filter needs to have a high pigment concentration. However, when a pattern is formed by a photolithography method using a colored photocurable composition with a high pigment concentration, the pigment absorbs ultraviolet exposure light in the exposure process, so that the lower layer portion of the photosensitive layer has an exposure amount of It becomes insufficient. That is, the lower layer portion of the colored layer is hard to be cured in the exposure process. So-called deep part curability cannot be obtained. As a result, the lower layer portion dissolves in the developing solution in the developing step, resulting in an overhang state, and the shape is easily undercut. There are also problems such as poor adhesion to the substrate.

  In order to improve the image quality of the liquid crystal display device, the colored curable composition must have a finer pigment and higher pigment concentration as described above. Finer pigments and higher pigment concentrations are more likely to cause undercuts and the like when forming colored pixels by photolithography. Production has been difficult, and this improvement is awaited.

  If an undercut occurs in the colored pixel after development, the colored pixel may be missing in the subsequent rinsing process, or the edge of the colored pixel may be rolled up in the post-baking process to form a square shape. Thickness unevenness occurs. If chipping occurs, coloring defects occur, and if film thickness unevenness occurs, the panels cannot be bonded together, or even if a panel can be created, liquid crystal alignment unevenness occurs, resulting in significant image quality degradation. End up. In an extreme case, an image cannot be obtained, or the transparent electrode ITO is disconnected, resulting in malfunction.

Conventionally, several techniques for suppressing the occurrence of such an undercut shape have been proposed.
One of them is a technology that suppresses undercut shape generation by adding an ultraviolet absorber to a photosensitive composition to reduce undercut after development and suppressing edge curl during firing (patent document). 1)

  As another proposal, by defining the average double bond equivalent in the organic compound formed by summing the binder resin and the polymerizable monomer in the photosensitive composition, and further specifying the molecular weight of the binder resin, A technique for forming a forward tapered shape is disclosed. (See Patent Document 2)

However, the above two technologies have the high color reproducibility required for television applications, and in the formation of colored pixels with a high pigment concentration such as a high-contrast color filter, the solubility in the unexposed portion of the developer is poor. Met. It was difficult to form a forward-tapered colored pixel while maintaining high adhesion, good developability, and adhesion to the substrate.
Japanese Patent No. 3329723 JP 2007-93811 A

The subject of the present invention is that, even if the pigment concentration is high, the exposed portion can be cured with sensitivity and a cured film having excellent adhesion to the substrate can be formed, and the developer solubility of the unexposed portion can be improved. It is an object of the present invention to provide a colored curable composition that is good, has no development residue, and can form a forward tapered pattern.
A further object of the present invention is to provide a color filter for a liquid crystal display device capable of realizing high color reproducibility and a high resolution solid-state imaging device by providing a colored region with the colored curable composition of the present invention. It is in.

Specific means for achieving the above object are as follows.
<1> A composition comprising a pigment, a polymer dispersant, an alkali-soluble resin, a polymerizable compound having at least one ethylenically unsaturated double bond in the molecule, a photopolymerization initiator, and a solvent. The pigment concentration with respect to the solid content of the product is in the range of 45 to 60% by mass, and the heat distortion temperature of the cured film formed by applying the curable composition and exposing at an exposure amount of 50 mJ / cm ² A colored curable composition having a temperature in the range of 100 to 200 ° C.
<2> The colored curable composition according to <1>, wherein the polymer dispersant is a polymer dispersant having an acid group.
<3> The colored curable composition according to <1> or <2>, further comprising a hydrogen donating compound.

<4> The colored curable composition according to any one of <1> to <3>, wherein the alkali-soluble resin and the polymer dispersant each have a weight average molecular weight in the range of 2,000 to 20,000. object.
<5> The content (M) of the polymerizable compound having at least one ethylenically unsaturated double bond in the molecule with respect to the total content (B) of the alkali-soluble resin and the polymer dispersant. The colored curable composition according to any one of <1> to <4>, wherein the mass ratio (M / B) is in the range of 0.3 to 0.6.
<6> Mass ratio (I / M) of the content (I) of the photopolymerization initiator to the content (M) of the polymerizable compound having at least one ethylenically unsaturated double bond in the molecule. Is in the range of 0.2 to 0.6, The colored curable composition according to any one of <1> to <5>.

<7> The crosslinking density in the cured film formed after applying the colored curable composition and exposing the dried coating film at 50 mJ / cm ² is in the range of 0.05 to 0.25. The colored curable composition according to any one of <1> to <6>, wherein:
<8> A color filter comprising a colored region formed of the colored curable composition according to any one of <1> to <7> on a substrate.
<9> A liquid crystal display device comprising the color filter according to <8>.

The heat distortion temperature referred to in the present invention is such that the colored curable composition is applied so that the film thickness after drying becomes 2.1 μm, dried (= after pre-baking at 100 ° C. for 80 seconds), and then exposed at 50 mJ / cm ² . Did. Thereafter, development and rinsing were performed, and the thermal deformation temperature of the colored layer after drying (25 ° C.) was examined by a needle penetration property from the film surface using a 2990 type micro thermal analyzer (TA Instruments).

  According to the configuration of the present invention, even in a high pigment concentration design, the developer solubility in the unexposed area is good, the sensitivity is excellent, the adhesion to the substrate is excellent, there is no development residue, and the forward taper of the pattern by baking. A colored curable composition capable of self-forming the shape is obtained. In addition, the colored curable composition of the present invention can provide a color filter for liquid crystal display devices with high color reproduction, and a color filter for a solid-state imaging device with high resolution.

  Hereinafter, the colored curable composition, the colored pattern forming method, the colored pattern, the color filter manufacturing method, the color filter, and the liquid crystal display element of the present invention will be described in detail.

<Colored curable composition>
The colored curable composition of the present invention includes a pigment, a polymer dispersant, an alkali-soluble resin, a polymerizable compound having at least one ethylenically unsaturated double bond in the molecule, a photopolymerization initiator, and a solvent. And may contain other components as necessary. In addition, in manufacture, it can disperse | distribute with a pigment, a polymer dispersing agent, a solvent, and other components in advance, and can be used as a pigment dispersion composition. Hereinafter, each component will be described in detail.

-Pigment-
As the pigment that can be used in the present invention, conventionally known various 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 considering 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 can be 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 Cl substituent was changed to OH Stuff, 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

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.

  If necessary, a dye can be used in combination for coloring. 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 includes 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.

  As content in the pigment dispersion composition of a pigment, 10-80 mass% is preferable with respect to the total solid (mass) of this composition, and 40-70 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.

-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 grinding as a highly viscous liquid composition together with the pigment, the water-soluble organic solvent, and the water-soluble inorganic salts. In the miniaturization step, in addition to the above components, a polymer dispersant, a pigment derivative, a low molecular dispersant and the like described later may be added.

  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 weight of the pigment, and a larger amount has a grinding effect, but a more preferred amount is 1 to 10 times the weight 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 to 300% by weight, preferably in the range of 100 to 200% by weight with respect to the pigment. Although there is no particular limitation on the operating conditions of the wet pulverizing apparatus in the present invention, the operating conditions in the case where the apparatus is a kneader are as follows. 200 rpm is preferable, and a relatively high rotation ratio between the two axes is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, 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.

-Pigment dispersion composition-
A method for producing a pigment dispersion composition is, for example, a method in which a pigment, a dispersant, and a solvent are mixed in advance and dispersed with a homogenizer or the like using a bead disperser using zirconia beads or the like. This can be done by dispersing.
As the dispersant used here, in addition to the polymer dispersant, a pigment derivative or a low molecular dispersant may be added as appropriate, or an alkali-soluble resin or the like may be added as necessary.

-Polymer dispersant-
The polymer dispersant that can be used in the present invention is a polymer compound having a polar group such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, and an amino group ammonium group. Among these dispersants, a polymer dispersant having an acid group such as a carboxyl group or a sulfonic acid group is preferably used, so that the solubility in an unexposed portion of the developer is improved and a forward tapered shape by post-baking is used. Can improve the self-forming property.

  Specifically, many types of compounds can be used. For example, (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (above Kyoeisha Chemical Co., Ltd.), EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (above Ciba Specialty Chemicals), DIS Polymer dispersants such as Perth Aid 6, Dispers Aid 8, Dispers Aid 15, Dispers Aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, Various Solsperse dispersants such as 28000 (manufactured by Nippon Lubrizol 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 (above, manufactured by Big Chemie Co., Ltd.). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  The molecular weight of the polymer dispersant is preferably 2,000 to 20,000. More preferably, it is 2,500-15,000, More preferably, it is 3,000-10,000. If the molecular weight is 2,000 or less, the linearity of the colored pattern may be lowered, and if the molecular weight is 20,000 or more, a forward taper may not be formed by post-baking.

  As content in the pigment dispersion composition of a polymer dispersing agent, 1-50 mass% is preferable with respect to the mass of a pigment, and 3-30 mass% is more preferable.

-Pigment derivative-
A pigment derivative is added to the pigment dispersion composition of the present invention as necessary. The pigment is introduced into the photocurable composition as fine particles by adsorbing the pigment derivative with a part having affinity with the dispersant or a polar group introduced onto the pigment surface and using this as the adsorption point of the dispersant. Therefore, the reaggregation can be prevented, and it is effective to construct 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 the dye derivative 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. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of the pigment derivative based on this invention, 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, the dispersion can be favorably performed while the viscosity is kept low, and the dispersion stability after dispersion can be improved. The color filter has high transmittance and high contrast.

-Alkali-soluble resin-
The alkali-soluble resin that can be used in the present invention is a linear organic polymer, and at least one alkali in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group that promotes solubility (for example, a carboxyl group, a phosphate group, a sulfonate group, etc.). 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 alkali-soluble 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 said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, it is described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., as well as in the side chain Preferred examples include acidic cellulose derivatives having a carboxylic acid, polymers having a hydroxyl group, an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  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 specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. 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 the (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, and 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. ], Etc. can be mentioned.

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. It is at least one, and particularly preferably CH ₂ ═CR ⁷ R ⁸ and / or CH ₂ ═C (R ⁷ ) (COOR ⁹ ).

  The amount of the alkali-soluble resin in the pigment dispersion composition is preferably 1 to 10% by mass, more preferably 2 to 8% by mass with respect to the pigment. However, the appropriate amount of the alkali-soluble resin should be judged as the content of the colored curable composition, which will be described later.

-Solvent-
In general, the pigment dispersion composition of the present invention can be suitably prepared using a solvent together with the above components.
Solvents 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, methyl lactate, lactic acid 3 such as ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate -Oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropion Ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2- Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

  Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl 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 and the like; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; aromatic hydrocarbons such as toluene and xylene.

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.

-Colored curable composition-
To the pigment dispersion composition obtained above, a polymerizable compound having at least one ethylenically unsaturated double bond in the molecule and a photopolymerization initiator are added, mixed, stirred, filtered and colored and cured. Adjusting the composition. At this time, at the time of preparing the pigment dispersion composition, an alkali-soluble resin and a solvent which are insufficient for a predetermined addition amount necessary for the colored curable composition can be additionally added and adjusted. Furthermore, components such as a hydrogen donating compound, a surfactant, and a polymerization inhibitor can be added as necessary.

  As content in the colored curable composition of alkali-soluble resin, 1-15 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-12 mass%, Most preferably 3 to 10% by mass. In consideration of the amount of the alkali-soluble resin already added to the pigment dispersion composition, it is added when adjusting the colored curable composition to adjust the deficiency. However, it does not deviate from the range of M / B ratio described later.

  The weight average molecular weight of the alkali-soluble resin is preferably 2,000 to 20,000. More preferably, it is 2,500-15,000, More preferably, it is 3,000-10,000. If the molecular weight is too small, the linearity of the colored pattern is lowered, which is not preferable. If the molecular weight is too large, the self-forming property of the forward taper deteriorates due to firing.

  Similarly, the amount of the solvent is finally adjusted in the adjustment step of the colored curable composition. The solid content of the colored curable composition is preferably 3 to 25% by mass, more preferably 10 to 22% by mass, and still more preferably 12 to 20% by mass.

-Preparation of pigment-(Color matching)
In the process of adjusting the colored curable composition, two or more kinds of pigments can be prepared to match the color characteristics. This can be prepared by blending pigment dispersion compositions containing the respective pigments, but by mixing and dispersing two or more pigment species in a pre-toned ratio, a pigment dispersion composition is prepared. You can keep it.

  For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture with an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. 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 100: 4 or less, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. Further, when the ratio is 100: 81 or more, the coloring power may decrease. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  Further, as the green pigment, one kind of halogenated phthalocyanine pigment can be used alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. . 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, when the ratio exceeds 100: 200, the dominant wavelength tends to be longer and the deviation from the NTSC target hue may become large. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. 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.

The amount of pigment (pigment concentration) relative to the solid content of the colored curable composition of the present invention is preferably 45 to 60% by mass, more preferably 45 to 55% by mass. Even if it is 45% by mass or less, the effect of the present invention is obtained, but the coloring power is small and not practical. If it exceeds 60% by mass, the flow characteristics of the colored curable composition will be deteriorated, and the formation of a colored pattern will be impossible due to insufficient sensitivity.
In addition, when using the pigment derivative shown below, the pigment concentration of the colored curable composition of the present invention is a value obtained by dividing the total mass of the pigment and the pigment derivative by the total solid content of the colored curable composition. Is used.

-Polymerizable compound having at least one ethylenically unsaturated double bond in the molecule-
The polymerizable compound having at least one ethylenically unsaturated double bond in the molecule (hereinafter sometimes referred to as “polymerizable compound” as appropriate) includes at least one addition-polymerizable ethylenically unsaturated group. A compound having a boiling point of 100 ° C. or higher at normal pressure is preferable, and a tetrafunctional or higher acrylate compound is more preferable.

Examples of the polymerizable compound include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, Methylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, tri Methylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethyl (Meth) acrylate after addition of ethylene oxide or propylene oxide to polyfunctional alcohol such as ethane, poly (meth) acrylate of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708, Japanese Patent Publication 50-6034, urethane acrylates described in JP-A-51-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, epoxy Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of a resin and (meth) acrylic acid.
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.

Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also 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 photopolymerizable composition having a very high photosensitive speed.

Commercially available products include 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.
Further, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.

A polymeric compound can be used in combination of 2 or more types, in addition to being used alone.
As the content of the polymerizable compound in the colored curable composition, the M / B ratio and the I / M ratio described later have priority. As long as this ratio is not impaired, the amount is preferably 3 to 55 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the total solid content of the composition. When the content of the polymerizable compound is within the above range, the curing reaction can be sufficiently performed.

-Photopolymerization initiator-
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as US Pat. No. 4,318,791 and European Patent Application No. 88050, US Pat. No. 4,199,420 Aromatic ketone compounds such as benzophenones described in the specification, (thio) xanthone-based or acridine-based compounds described in the specification of French Patent No. 2456741, coumarin-based or vinyl compounds described in JP-A-10-62986 Imidazole compounds, sulfoniums such as JP-A-8-015521 Machine boron complex, etc., etc. can be mentioned.

  Examples of the photopolymerization initiator include acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, active halogen compounds (triazine series, halomethyloxadiazole series, coumarin series), acridine series, biimidazole series. And oxime ester systems are preferred.

  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.

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

  Preferred examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and the like. 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 (triazine, oxadiazole, coumarin) 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, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) ) -S-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloro Methyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, 3-methyl- -Amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl A preferred example is -5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin.

  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 this invention, it is not limited to the above photoinitiator, Other well-known things 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 triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; 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.
Moreover, these photoinitiators can also be used together.

As content in the photocurable composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5-5.0. % By 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. R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. 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 the general formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —, where L ³ represents —O— or —S—. W is as defined 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 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 represents 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 and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ and A ⁴ and adjacent carbon atoms, and R ⁶¹ and R ⁶² each independently represent a monovalent group. Can be 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 ) — R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and A, R ¹ , R ² , and R ³ are Can be bonded to each other to form an aliphatic or aromatic ring.)

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-alkylsulfinamoyl Group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfa Moyl 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 conjugated 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 as a particularly preferred example of the heteroaryl ring in the heteroaryl group, 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 hetero ring which may have a substituent, and specific examples of the aromatic ring or hetero 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.).

  In the general formula (XVIII) described above, among the examples of the nitrogen-containing or sulfur-containing heterocycle formed by Y together with the above-mentioned A and the adjacent carbon atom, 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 or 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 nonmetallic atomic group, and A and R ¹ , R ⁴ , R ⁵ and R ⁶ are bonded to each other to form an aliphatic group. 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 the general formula (XVIII-3), which is a preferred embodiment of the compound represented by the general 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 thereto. 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 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 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total solid content of the colored photosensitive composition for a color filter of the present invention. More preferably, it is 0.1-5 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.

<Hydrogen donating compound>
The colored curable composition of the present invention preferably contains a hydrogen donating compound. In the present invention, the hydrogen-donating compound has functions such as further improving the sensitivity of the sensitizing dye and initiator to actinic radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen. By using a hydrogen-donating compound, exposure sensitivity and substrate adhesion are improved, and the development latitude is widened. In addition, there is an effect that a pattern cross section is formed in a forward tapered shape in a post-bake process.

Examples of such hydrogen donating compounds include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. , JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like. Moreover, mercapto compounds having a heterocyclic ring such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, and aliphatic polyfunctional mercapto compounds.
A hydrogen donor compound may be used individually by 1 type, and may use 2 or more types together.

Next, the preferable ratio range between each component in a colored curable composition is demonstrated.
The mass ratio (= M / B) of the polymerizable compound (M) to the total (B) of the alkali-soluble resin and the polymer dispersant is preferably 0.3 to 0.6. More preferably, it is 0.35-0.55, More preferably, it is 0.4-0.5. When the M / B ratio is 0.3 or less, the adhesion to the substrate is lowered, and the development latitude is narrowed. When the M / B ratio is 0.6 or more, the solubility of the unexposed portion in the developer is lowered, and the post tape is not self-formed in a forward tapered shape.

The mass ratio (= I / M) of the photopolymerization initiator (I) to the total amount (M) of the polymerizable compound is preferably 0.2 to 0.6, more preferably 0.25 to 0.55. More preferably, it is 0.3-0.5. When the I / M ratio is 0.2 or less, the adhesion to the substrate is lowered, and further, self-forming in a forward tapered shape is not performed by post-baking. On the other hand, when the I / M ratio is 0.5 or more, the hardened portion is thick with respect to the mask width, making it impossible to form a fine pattern.
In the present invention, the amount of sensitizing dye is not included in the amount of photopolymerization initiator.

In the present invention, the thermal deformation temperature was measured using a 2990 type micro thermal analyzer (manufactured by TA Instruments).
The colored curable composition of the present invention was applied so that the film thickness after drying was 2.1 μm, dried (after pre-baking at 100 ° C. for 80 seconds), and then exposed to 50 mJ / cm ² . Thereafter, development, rinsing, and the thermal deformation temperature of the colored layer after drying (25 ° C.) were examined by using a 2990 type micro thermal analyzer (TA Instruments Co., Ltd.) according to the needle penetration characteristics from the surface under the following conditions. .
Weight: about 5 μN (45 nA), temperature rising rate: 15 ° C./sec, room temperature to 250 ° C.
The temperature at which the needle penetration amount reaches 0.5 μm from the surface corresponds to the heat distortion temperature in the present invention.

  The heat distortion temperature of the colored curable composition of the present invention is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and further preferably 120 to 180 ° C. When the heat distortion temperature is less than 100 ° C., a forward taper pattern can be obtained by post baking, but this is not preferable because the change in pixel size before and after post baking becomes large. A thermal deformation temperature of 200 ° C. or higher is not preferable because the thermal polymerization reaction hinders thermal deformation of the pattern.

In the present invention, the crosslinking density is a numerical value obtained by multiplying the double bond density of the polymerizable compound by the double bond consumption rate, and is defined as follows.
(Crosslinking density) = (number of functional groups × double bond consumption rate (%) / weight average molecular weight of polymerizable compound) × (ratio of the polymerizable compound in the total solid content)
The consumption rate of the double bond was measured using a Nicolet 6700 (manufactured by Thermo Fisher SCIENTIFIC) for the colored layer before and after 50 mJ / cm ² exposure, and the peak area corresponding to the C═C double bond in the vicinity of 810 cm ^−1. Calculated from changes in

Among the polymerizable compounds, those having a crosslinking density by exposure of 0.05 to 0.25 are preferable in terms of self-formability of forward taper by post-baking. More preferably, it is 0.07-0.23, More preferably, it is 0.10-0.20.
If the crosslinking density is less than 0.05, the adhesion to the substrate is deteriorated and the development latitude becomes narrow, which is not preferable. On the other hand, when the crosslink density is larger than 0.25, the forward taper self-forming property by post-baking deteriorates.

<Other ingredients>
In the colored curable composition of the present invention, if necessary, a fluorosurfactant, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, and a polymer compound other than the above alkali-soluble resin In addition, various additives such as other surfactants, adhesion promoters, antioxidants, ultraviolet absorbers and anti-aggregation agents can be contained.

-Fluorosurfactant-
By containing a fluorosurfactant, the liquid properties (particularly fluidity) of the coating liquid can be improved, and the uniformity of the coating thickness and the liquid-saving property can be improved. That is, the interfacial tension between the substrate and the coating liquid is reduced to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several μm is formed with a small amount of liquid. This is also effective in that a film having a uniform thickness with small thickness unevenness can be formed.

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

    As the fluorosurfactant, 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, 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 Limited), Asahi Guard AG7105, 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, 8 2 (manufactured by JEMCO (Ltd.)), and the like.

  The fluorine-based surfactant is particularly effective in preventing coating unevenness and thickness unevenness when the coating film is thinned. Further, it is also effective in slit coating that is liable to cause liquid breakage.

  0.001-2.0 mass% is preferable with respect to the total mass of a colored curable composition, and, as for the addition amount of a fluorine-type surfactant, More preferably, it is 0.005-1.0 mass%.

-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. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

-Thermal polymerization component-
It is also effective to contain a thermal polymerization component in the colored curable composition of the present invention. If necessary, an epoxy compound can be added to increase the strength of the coating film. 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, etc. Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (manufactured by Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (manufactured by Daicel Chemical) and their similar The bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UCB) can also be used. As cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. (above manufactured by Nagase Kasei), Examples of cycloaliphatic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT- 401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 (manufactured by Toto Kasei) and the like. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine type epoxy resins, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resins can be used.

-Other surfactants-
The colored curable composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coatability. In addition to the above-mentioned fluorosurfactants, nonionic, cationic, and anionic Various surfactants of the system can be used. Among these, the above-mentioned fluorine-based surfactants and nonionic surfactants are preferable.

  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 Kasei Co., Ltd. It can be used as appropriate. In addition to the above, the aforementioned dispersants can also be used.

  In addition to the above, various additives can be added to the colored curable composition. Specific examples of additives include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and anti-aggregation 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 developability of the colored curable composition is further improved, the colored curable composition has an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid can be 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, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, 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.

-Thermal polymerization inhibitor-
In addition to the above, it is preferable to add a thermal polymerization inhibitor in addition to the above, for example, 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-t-butylphenol), 2-mercaptobenzimidazole, etc. Useful.

-Colored curable composition and method for producing color filter using the same-
The colored curable composition of the present invention contains an alkali-soluble resin, a polymerizable compound, and a photopolymerization initiator (preferably together with a solvent) in the pigment dispersion composition of the present invention described above, and if necessary, It can be prepared by mixing an additive such as a surfactant and mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably includes kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

An example of the manufacturing method of the colored curable composition of this invention is shown below.
A mixture of a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt is mixed with a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder, etc. Is used to grind the pigment while applying a strong shearing force, and the mixture is put into water and made into a slurry with a stirrer or the like. Subsequently, this slurry is filtered and washed with water to remove the water-soluble organic solvent and the water-soluble inorganic salt, and then dried to obtain a refined pigment.

The beads are dispersed with a pigment and a dispersant and / or a pigment derivative and a solvent. Using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., fine dispersion with beads made of 0.01 to 1 mm particle size glass, zirconia, etc., pigment dispersion composition Get. It is also possible to omit the process of making the pigment fine.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.
And a photopolymerizable compound, a photoinitiator, an alkali-soluble resin, etc. are added to the pigment dispersion composition obtained as mentioned above, and the photocurable composition of this invention is obtained.

The colored curable composition of the present invention is applied to a substrate directly or through another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, etc., and a photocurable coating film The film is exposed through a predetermined mask pattern, and after the exposure, the uncured portion is developed and removed with a developer to form a pattern film composed of pixels of each color (three colors or more), and a color filter It can be.
In this case, ultraviolet rays such as g-line, h-line, i-line and j-line are particularly preferable as the radiation to be used. The color filter for the liquid crystal display device is preferably an exposure using a high-pressure mercury lamp as a light source and mainly using h-line and i-line in a proximity exposure machine and a mirror projection exposure machine. As an exposure amount, 20-400 mJ / cm < ² > is preferable, More preferably, it is 30-200 mJ / cm < ² >.
In a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine.

  The color filter of the present invention is formed on a substrate such as glass by using the above-described photocurable composition of the present invention, and the photocurable composition of the present invention is directly or via other layers. Then, after forming a coating film on the substrate by, for example, slit coating, the coating film is dried, subjected to pattern exposure, and development processing using a developer can be sequentially performed. Thereby, the color filter used for a liquid crystal display device or a solid-state image sensor has few process difficulties, and can be manufactured with high quality and low cost.

Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these substrates, and solid-state imaging devices. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate, and a plastic substrate. On these substrates, usually, a black matrix for isolating each pixel is formed, or a transparent resin layer is provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface. In addition, the photo-curing property of the present invention is also applied to 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 arranged. A color filter can be prepared by forming a patterned film made of the composition. The photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel. Examples of the substrate in the TFT liquid crystal driving substrate include glass, silicon, 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 a TFT liquid crystal driving substrate or a surface of the driving substrate can be used.

  A method for applying the colored curable composition of the present invention to a 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 referred to as a slit nozzle coating method). Is preferred. 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, when a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. The discharge amount of the colored curable composition from the slit nozzle is usually 500 to 2000 microliter / second, preferably 800 to 1500 microliter / second, and the coating speed is usually 50 to 300 mm / second. , Preferably it is 100-200 mm / sec. The solid content of the colored curable composition is usually 10 to 20%, preferably 13 to 18%. When forming a coating film with the colored curable composition of the present invention on a substrate, the thickness of the coating film (after pre-baking treatment) is generally 0.3 to 5.0 μm, preferably 0.5 to 4 0.0 μm, most preferably 0.8 to 3.0 μm.

Usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking. As the conditions for vacuum drying, the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed in a temperature range of 50 to 140 ° C., preferably about 70 to 110 ° C., using a hot plate, an oven, or the like, and can be performed under conditions of 10 to 300 seconds. High frequency treatment or the like may be used in combination. High frequency processing can be used alone.

The exposure is performed by a proximity exposure machine and a mirror projection exposure machine through a mask. As an exposure amount, 20-400 mJ / cm < ² > is preferable, More preferably, it is 30-200 mJ / cm < ² >.

In the development process, the uncured portion after the exposure is eluted in the developer, and only the cured portion remains. 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.

As said organic solvent, the above-mentioned solvent which can be used when preparing the colored curable composition of this invention is mentioned.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentrations of alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by 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. It is also possible to develop with the substrate tilted.
In the case of a solid-state image sensor, paddle development is also used.

After the development processing, after a rinsing step for washing and removing excess developer, drying is performed, and then heat treatment (post-baking) is performed to complete the curing.
The rinsing process is usually performed with pure water. However, to save liquid, pure water is used in the final cleaning. At the beginning of cleaning, used pure water is used, the substrate is tilted and cleaned, and ultrasonic irradiation is performed. Can be used together.

After rinsing, draining and drying are performed, and then a heat treatment is 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 a formula.
By sequentially repeating the above operation for each color in accordance with the desired number of hues, a color filter formed with a plurality of colored cured films can be produced.

Although the application of the colored curable composition of the present invention has been described mainly focusing on the application to a color filter, it can also be applied to the formation of a black matrix that isolates each colored pixel constituting the color filter.
The black matrix exposes and develops the colored curable composition of the present invention using a black pigment such as carbon black or titanium black as a pigment, and then further post-bake as necessary to promote film curing. Can be formed.

  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, “part” is based on mass.

Example 1
1. Adjustment of pigment dispersion Blue pigment C.I. I. 200 parts of Pigment Blue 15: 6, 1600 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, the kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a blue pigment were obtained.

  The purple pigment C.I. I. 200 parts of Pigment Violet 23, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, the kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a violet pigment were obtained.

With the following composition, using a homogenizer, the rotational speed was 3,000 r. p. m. And stirred for 3 hours to prepare a mixture.
[Composition 1]
Pigment Blue 15: 6 (average primary particle diameter 25 nm) 90 parts Pigment Violet 23 (average primary particle diameter 25 nm) 10 parts Phthalocyanine derivative (Solsperse 5000 manufactured by Avicia) 10 parts benzyl methacrylate / methacrylic acid (= 70 / 30 [molar ratio]) copolymer (weight average molecular weight: 5,000) in propylene glycol monomethyl ether acetate solution (solid content 40%) 75 parts Dispersant (Adisper PB-821 (Ajinomoto Fine Techno Co., Ltd. amine value) 9, acid value 13)) 40 parts propylene glycol monomethyl ether acetate 495 parts

  Subsequently, the mixture obtained above was further subjected to a dispersion treatment for 6 hours in a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) using 0.1 mmφ zirconia beads to obtain a pigment dispersion composition.

2. Preparation of colored curable composition To the obtained pigment dispersion composition, components having the following composition were further added and mixed by stirring to prepare a colored curable composition 1.

[Composition 2]
・ Dipentaerythritol hexaacrylate 30 parts ・ 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (photopolymerization initiator) 10 parts ・ 4,4′-bis (diethylamino) benzophenone 5 parts (sensitization) Pigment)
2-mercaptobenzothiazole 5 parts (hydrogen donating compound)
Propylene glycol monomethyl ether acetate 230 parts The pigment concentration in the total solid content of this colored curable composition 1 was 48% by mass, and M / B = 0.43 and I / M = 0.33.

(Example 2)
1. Preparation of pigment dispersion Green pigment C.I. I. 200 parts of Pigment Green 36, 1600 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, the kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a green pigment were obtained.

  The yellow pigment C.I. I. 200 parts of Pigment Yellow 150, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, the kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a violet pigment were obtained.

With the following composition, using a homogenizer, the rotational speed was 3,000 r. p. m. And stirred for 3 hours to prepare a mixture.
[Composition 3]
Pigment Green 36 (average primary particle diameter 25 nm) 70 parts Pigment Yellow 150 (average primary particle diameter 25 nm) 30 parts phthalocyanine derivative (Solsperse 5000 manufactured by Avicia) 10 parts benzyl methacrylate / methacrylic acid (= 70/30 [ Molar ratio]) 75 parts of propylene glycol monomethyl ether acetate solution of copolymer (weight average molecular weight: 5,000) (solid content 40%) Dispersant (Ajisper PB-821 (Ajinomoto Fine Techno Co., Ltd., amine number 9, Acid value 13)) 40 parts ・ Propylene glycol monomethyl ether acetate 495 parts

  Subsequently, the mixture 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 composition.

2. Preparation of colored curable composition To the obtained pigment dispersion composition, components having the following composition were further added and mixed by stirring to prepare a colored curable composition 2.

[Composition 4]
・ Dipentaerythritol hexaacrylate 30 parts ・ 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (photopolymerization initiator) 10 parts ・ 4,4′-bis (diethylamino) benzophenone 5 parts (sensitization) Pigment)
2-mercaptobenzothiazole 5 parts (hydrogen donating compound)
Propylene glycol monomethyl ether acetate 230 parts The pigment concentration in the total solid content of this colored curable composition 2 was 48%, and M / B = 0.43 and I / M = 0.33.

(Example 3)
1. Preparation of pigment dispersion Red pigment C.I. I. 200 parts of Pigment Red 254, 1600 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, the kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a red pigment were obtained.

  The red pigment C.I. I. 200 parts of Pigment Red 177, 2000 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 8 hours. Next, the kneaded product is poured into 10 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 60 ° C. overnight. 190 parts of a red pigment were obtained.

With the following composition, using a homogenizer, the rotational speed was 3,000 r. p. m. And stirred for 3 hours to prepare a mixture.
[Composition 5]
Pigment Red 254 (average primary particle diameter 25 nm) 90 parts Pigment Red 177 (average primary particle diameter 25 nm) 10 parts Diketopyrrolopyrrole derivative (sulfonated diketopyrrolopyrrole pigment)
10 parts benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 5,000) propylene glycol monomethyl ether acetate solution (solid content 40%) 75 parts PB-821 (Ajinomoto Fine Techno Co., Ltd., amine number 9, acid value 13)) 40 parts / propylene glycol monomethyl ether acetate 495 parts

  Subsequently, the mixture obtained above was further subjected to co-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 composition.

  Components of the following composition were further added to the obtained pigment dispersion composition, and the mixture was stirred and mixed to prepare a colored curable composition 3.

〔composition〕
Dipentaerythritol hexaacrylate (polymerizable compound) 30 parts 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (photoinitiator) 10 parts 4,4'-bis (diethylamino) benzophenone 5 parts (sensitizing dye)
2-mercaptobenzothiazole 5 parts (hydrogen donating compound)
Propylene glycol monomethyl ether acetate 310 parts The pigment concentration in the total solid content of this colored curable composition 3 was 48%, and M / B = 0.43 and I / M = 0.33.

(Comparative Example 1)
A colored curable composition 4 was obtained in the same manner as in Example 2 except that the dispersant was changed to (DISPERBYK-2025 (manufactured by Big Chemie Japan) amine value 37, acid value 38).
(Comparative Example 2)
A colored curable composition 5 was obtained in the same manner as in Example 2 except that the polymerizable compound was changed to EA-1025 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
(Comparative Example 3)
A colored curable composition 6 was obtained in the same manner as in Example 2 except that the polymerizable compound was changed to M-305 (manufactured by Toagosei Co., Ltd.).
(Comparative Example 4)
In Example 1, the pigment concentration in the total solid content of the colored curable composition was set to 48%, M / B = 0.28, and I / M = 0.33. A colored curable composition 7 was obtained in the same manner as in Example 1 except that mercaptobenzoxazole and NK ester A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) were used as the polymerizable compound.
(Comparative Example 5)
In Example 1, the pigment concentration in the total solid content of the colored curable composition was set to 48%, M / B = 0.63, I / M = 0.33, and prepared as a hydrogen-donating compound. A colored curable composition 8 was obtained in the same manner as in Example 1 except that mercaptobenzoxazole and NK ester A-TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.) were used as the polymerizable compound.
(Comparative Example 6)
In Example 3, the pigment concentration in the total solid content of the colored curable composition was set to 48%, M / B = 0.43, and I / M = 0.18. A colored curable composition 9 was obtained in the same manner as in Example 3 except that phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime was used.
(Comparative Example 7)
In Example 3, the pigment concentration in the total solid content of the colored curable composition was set to 48%, M / B = 0.43, and I / M = 0.65. A colored curable composition 10 was obtained in the same manner as in Example 3 except that phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime was used.
(Comparative Example 8)
A colored curable composition 11 was obtained in the same manner as in Example 2 except that the dispersant was changed to (Ajisper PB-711 (Ajinomoto Fine Techno Co., amine value 45, no acid group)).
(Comparative Example 9)
The same method as in Example 2 except that 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (photopolymerization initiator) was added instead of adding 2-mercaptobenzothiazole (hydrogen donor compound). A colored curable composition 12 was obtained. In this case, M / B = 0.43 and I / M = 0.5.
(Comparative Example 10)
Instead of adding a propylene glycol monomethyl ether acetate solution (solid content 40%) of a benzyl methacrylate / methyl methacrylate (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 5,000), benzyl methacrylate / methyl methacrylate (= 70/30 [molar ratio]) Implementation was carried out except that a pigment dispersion composition was prepared by adding a propylene glycol monomethyl ether acetate solution (solid content 40%) of a copolymer (weight average molecular weight: 30,000). A colored curable composition 13 was obtained in the same manner as in Example 2.
Example 4
In Example 1, the pigment concentration in the total solid content of the colored curable composition was set to 48%, M / B = 0.36, and I / M = 0.33. A colored curable composition 14 was obtained in the same manner as in Example 1 except that dimethylaminobenzoic acid ethyl ester was used.
(Example 5)
In Example 1, the pigment concentration in the total solid content of the colored curable composition was set to 48%, M / B = 0.54, and I / M = 0.33. A colored curable composition 15 was obtained in the same manner as in Example 1 except that dimethylaminobenzoic acid ethyl ester was used.
(Example 6)
In Example 3, the pigment concentration in the total solid content of the colored curable composition was set to 48%, M / B = 0.43, and I / M = 0.28. A colored curable composition 16 was obtained in the same manner as in Example 3 except that methoxy-4-methyl-6-trichloromethyl-S-triazine was used.
(Comparative Example 7)
In Example 3, the pigment concentration in the total solid content of the colored curable composition was set to 48%, M / B = 0.43, and I / M = 0.53. A colored curable composition 17 was obtained in the same manner as in Example 3 except that methoxy-4-methyl-6-trichloromethyl-S-triazine was used.

The heat distortion temperature of the colored curable compositions 1 to 17 prepared as described above was measured by the following method.
<Heat deformation temperature>
The heat distortion temperature was measured using a 2990 type micro thermal analyzer (TA Instruments).
The colored curable composition of the present invention was applied so that the film thickness after drying was 2.1 μm, dried (after pre-baking at 100 ° C. for 80 seconds), and then exposed to 50 mJ / cm ² . Thereafter, development, rinsing, and the thermal deformation temperature of the colored layer after drying (25 ° C.) were examined by using a 2990 type micro thermal analyzer (TA Instruments Co., Ltd.) according to the needle penetration characteristics from the surface under the following conditions. .
Weight: about 5 μN (45 nA), temperature rising rate: 15 ° C./sec, room temperature to 250 ° C.
The temperature at which the needle penetration amount reaches 0.5 μm from the surface corresponds to the heat distortion temperature in the present invention. The results are summarized in Table 1. In Table 1, “> 250” indicates that the heat distortion temperature was 250 ° C. or higher.

-Formation of colored curable composition layer-
The colored curable composition obtained as described above was slit-coated on a 550 mm × 650 mm glass substrate under the following conditions. A colored curable composition layer was formed by vacuum drying and pre-baking (100 ° C., 80 seconds).

(Slit application conditions)
Gap at the opening of the coating head tip: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry film thickness): 2.0 μm
Application temperature: 23 ° C

-Exposure and development-
The obtained coated substrate was irradiated with an exposure amount of 50 mJ / cm ² in a pattern through a mask using an ultrahigh pressure mercury lamp with an energy of 20 mW / cm ^{2 as} a light source, and after exposure, The entire surface of the coating film was shower-developed with a 1.0% aqueous solution of KOH-based developer (trade name: CDK-1, manufactured by Fuji Film Electronics Materials Co., Ltd.) and washed with pure water.

  The developed coating film was heated in an oven at 230 ° C. for 0.5 hour (post-baking). Thereby, a colored pattern was formed on the glass substrate to obtain a color filter.

-Evaluation-
The exposure sensitivity, crosslink density, developability of the colored curable composition layer formed on the glass substrate, the substrate adhesion of the colored pattern obtained after patterning, and the cross-sectional shape of the colored pattern were evaluated as follows. The results are summarized in Table 1.

<Exposure sensitivity of colored curable composition layer>
The minimum exposure amount in which the film thickness after development of the exposed region was 95% or more with respect to 100% of the film thickness before exposure was evaluated as exposure sensitivity. A smaller exposure sensitivity value indicates higher sensitivity.

<Crosslinking density of colored curable composition layer>
The double bond (unsaturated bond) consumption rate of the exposed area was measured using a Nicolet 6700 (manufactured by Thermo Fisher SCIENTIFIC) for the colored layer before and after exposure of 50 mJ / cm ² , and C = C 2 near 810 cm ^−1. It was calculated from the change in peak area corresponding to the double bond. Using this value, the crosslinking density was calculated from the above formula. The results are shown in Table 1.

-Developer solubility in unexposed areas, developability, adhesion to substrate, pattern cross-sectional shape-
The substrate surface after post-baking and the cross-sectional shape were confirmed by an ordinary method using an optical microscope and SEM photograph observation to evaluate developability, substrate adhesion, and pattern cross-sectional shape, and are summarized in Table 1. Details of the evaluation method are as follows.

<Developer solubility>
In the exposure process, the behavior when the region not irradiated with light (unexposed portion) was dissolved in the developer was evaluated.
○: Developed in a soluble manner.
X: The film was developed like a film.

<Developability>
In the exposure process, the presence or absence of a residue on the glass substrate in an unexposed region (unexposed portion) was observed to evaluate developability.
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but it was practically unproblematic.
X: Residue was remarkably confirmed in the unexposed part.

<Adhesion with substrate>
As an evaluation of adhesion to the substrate, it was observed whether or not a pattern defect occurred. The evaluation items were evaluated based on the following criteria.
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

<Pattern cross-sectional shape>
The cross-sectional shape of the formed pattern was evaluated according to the following criteria.
A: Tapered angle in the range of 30 to less than 70 degrees (forward taper)
○: Tapered angle in the range of 70 to less than 85 degrees (forward taper)
Δ: Range of taper angle of 85 to 90 degrees (rectangular)
X: The taper angle exceeds 90 degrees (reverse taper)

From Table 1, the colored curable composition of the present invention having a heat distortion temperature in the range of 100 to 200 ° C. is excellent in any of exposure sensitivity, developer solubility, developability, adhesion to the substrate, and pattern cross-sectional shape. The crosslink density was found to be appropriate.
It was found that particularly excellent results were obtained when a polymer dispersant having an acid group and a hydrogen-donating compound were used and the M / B, I / M, and crosslinking density were within a certain range.

Claims (9)

A composition comprising a pigment, a polymer dispersant, an alkali-soluble resin, a polymerizable compound having at least one ethylenically unsaturated double bond in the molecule, a photopolymerization initiator, and a solvent, The pigment concentration with respect to the minute is in the range of 45-60 mass%, and the heat distortion temperature of the cured film formed by applying the curable composition and exposing at an exposure amount of 50 mJ / cm ² is 100- A colored curable composition having a range of 200 ° C.   The colored curable composition according to claim 1, wherein the polymer dispersant is a polymer dispersant having an acid group.   Furthermore, the colored curable composition of Claim 1 or Claim 2 containing a hydrogen donating compound.   The colored curable composition according to any one of claims 1 to 3, wherein the alkali-soluble resin and the polymer dispersant each have a weight average molecular weight in the range of 2,000 to 20,000.   Mass ratio of the content (M) of the polymerizable compound having at least one ethylenically unsaturated double bond in the molecule to the total content (B) of the alkali-soluble resin and the polymer dispersant (B) The colored curable composition according to any one of claims 1 to 4, wherein M / B) is in the range of 0.3 to 0.6.   The mass ratio (I / M) of the content (I) of the photopolymerization initiator to the content (M) of the polymerizable compound having at least one ethylenically unsaturated double bond in the molecule is 0. The colored curable composition according to any one of claims 1 to 5, wherein the colored curable composition is in a range of .2 to 0.6. The crosslinking density in the cured film formed after applying the colored curable composition and exposing the dried coating film at 50 mJ / cm ² is in the range of 0.05 to 0.25. The colored curable composition according to any one of claims 1 to 6.   A color filter comprising a colored region formed of the colored curable composition according to any one of claims 1 to 7 on a substrate.   A liquid crystal display device comprising the color filter according to claim 8.