JP5235558B2 - Curable coloring composition, color filter, and liquid crystal display device using color filter - Google Patents

Description

The present invention, hardening coloring composition, a color filter, and a liquid crystal display device using a color filter.

In recent years, with the increase in screen size of TVs and other devices, the size of pixels has increased, and production efficiency has advantages compared to the photolithographic method. Expected as a law, many methods are disclosed.
Further, color filters for TV use are required to have advanced color characteristics such as contrast, and finer organic pigments as colorants have been used.

As the above method, a resin composition for an ink jet color filter containing a solvent having a boiling point of 250 ° C. or higher, a binder resin, and a colorant is disclosed (for example, see Patent Document 1).
However, since the boiling point of the solvent used is too high, flatness in the drying process can be ensured, but since the binder resin has a large molecular weight, the viscosity is high and a stable discharge performance of the resin composition cannot be obtained.

Also, an aqueous color filter ink containing 60% by weight or more of a solvent having a boiling point of 150 to 250 ° C. and one or more of glycerin, diethylene glycol, and ethylene glycol is disclosed (see, for example, Patent Document 2). .
However, although the boiling point of the solvent is 150 ° C. to 250 ° C., those actually exemplified are PGMEA (boiling point 146 ° C.), EEP (boiling point 170 ° C.), and hydrophilic glycerin as a wetting agent. And the flatness of the colored layer was inferior.

Further, there is a method in which a thermosetting ink composition for a color filter containing a binder and an epoxy group-containing monomer is used as a first aspect, and a composition that defines wettability and specifies a solvent type is a second aspect. (For example, refer to Patent Document 3).
However, since it is an ink composition containing an ether bond, a solvent having an OH group or the like to ensure wettability to the substrate, or a solvent containing a diethylene glycol-based ether bond, the reliability as a color filter, The dispersion stability was deteriorated.
Furthermore, an ink set for a color filter that is an active energy ray-curable ink containing a pigment containing R, G, and B, and a monofunctional and polyfunctional monomer is disclosed (for example, see Patent Document 4).
However, the dispersibility of the pigment as the colorant is not sufficient, and the performance (for example, contrast, etc.) when the color filter obtained using the ink set is made into a panel is inferior. In addition, there is a problem that clogging of the ink jet nozzle is likely to occur.
As the physical properties of the curable composition, there is a demand for a smooth pattern without uniformity of coating film (uniformity of film thickness) and unevenness. However, the use of a silane coupling agent is known to improve the adhesion to the substrate, but the present situation is that the film thickness uniformity required for the flat panel cannot be ensured.
JP 2000-310706 A JP-A-11-202114 JP 2001-350012 A JP 2002-371216 A

The object of the present invention, which has been made in consideration of the problems in the prior art, is excellent in high dispersibility and high dispersion stability of the colorant even when the colorant is contained in a high concentration, and suitable for slit coating. There are, to suppress the occurrence of aggregation foreign matter into the ink jet nozzle or the like, is to provide a hardening coloring composition having excellent thickness uniformity.
Another object of the present invention is to provide a high brightness and high contrast color filter using the curable coloring composition of the present invention, and a liquid crystal display device using the same.

<1> Curability characterized by containing a colorant, a dispersant, a solvent, a polymerizable compound, a polymerization initiator, and a resin, and containing 1 to 50% by mass of tetrahydrofurfuryl acetate . Coloring composition.
<2> The curable coloring composition according to <1>, wherein the solvent has a boiling point of less than 160 ° C. at a normal pressure of 20 to 80% by mass in the total amount of the solvent.
<3> The curable coloring composition as described in <1> or <2> above, wherein 10 to 40% by mass of a solvent having a boiling point of 160 ° C. or higher and lower than 190 ° C. at normal pressure is contained in the total amount of the solvent. .

<4 > The curable coloring composition according to any one of <1> to <3>, wherein the resin is an alkali-soluble resin.
< 5 > A color filter comprising a colored layer produced using the curable coloring composition according to any one of <1> to <4> .
< 6 > A liquid crystal display device comprising the color filter according to < 5 >.

According to the present invention, even when the colorant is contained in a high concentration, the colorant is excellent in high dispersibility and high dispersion stability, suitable for slit coating, suppressing occurrence, it is possible to provide a hardening coloring composition having excellent thickness uniformity.
In addition, a high brightness and high contrast color filter using the curable coloring composition of the present invention, and a liquid crystal display device using the same can be provided.

  Hereinafter, the coloring composition of the present invention, the curable coloring composition, the color filter produced using the curable coloring composition, and the liquid crystal display device produced using the color filter will be described in detail.

[Coloring composition]
The coloring composition of the present invention contains a colorant, a dispersant, and a solvent, and contains 1 to 50% by mass of tetrahydrofurfuryl acetate.
Hereinafter, each component will be described.

<Solvent>
As the solvent that can be used in the present invention, a general organic solvent can be used as long as the effect when applied to a colored composition or a curable colored composition is not impaired. 1-50 mass%. More preferably, tetrahydrofurfuryl acetate is contained in the total amount of the composition in an amount of 3 to 40% by mass, and more preferably 5 to 30% by mass. By containing tetrahydrofurfuryl acetate in the above range, it is excellent in dispersion stability and suppresses the generation of aggregated foreign matters.

  Examples of the solvent other than tetrahydrofurfuryl acetate that can be used in the present invention include liquids selected from the organic solvents shown below. The solubility of each component contained in the pigment dispersion and the curable composition However, it is not particularly limited as long as these desired physical properties are satisfied, but it is preferably selected in consideration of safety.

  Specific examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl oxyacetate, and ethyl oxyacetate. , Butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxypropion Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropion Ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy-2 -Methyl 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 (ethylene glycol monomethyl ether acetate), ethyl cellosolve acetate (ethylene glycol monoethyl ether acetate), diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, pro Etc. glycol propyl ether acetate;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene and xylene are preferred.

In this invention, the aspect which contains 20-80 mass% of solvents whose boiling point in a normal pressure is less than 160 degreeC in the solvent whole quantity in a coloring composition is preferable. More preferably, it is 30-75 mass%, More preferably, it is 40-70 mass%.
By including a solvent having a boiling point of less than 160 ° C. at normal pressure in the above range, the drying time is shortened and the productivity is excellent.

Examples of the solvent having a boiling point under atmospheric pressure of less than 160 ° C. include the following, but the present invention is not limited thereto.
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 2-peptanone, n-butyl acetate, i-butyl acetate, i-pentyl acetate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, pyrubin Examples thereof include ethyl acid, cyclohexanone and the like, and among them, propylene glycol monomethyl ether acetate (boiling point: 146 ° C), propylene glycol monomethyl ether (boiling point: 121 ° C), and cyclohexanone (boiling point: 156 ° C) are preferable.
These solvents may be used alone or in combination of two or more.

Moreover, in this invention, the aspect which contains 10-40 mass% of solvents whose boiling point in a normal pressure is 160 degreeC or more and less than 190 degreeC in the solvent whole quantity in a coloring composition is preferable. More preferably, it is 10-35 mass%, More preferably, it is 10-30 mass%.
By containing a solvent having a boiling point of 160 ° C. or more and less than 190 ° C. in the above range, drying of the slit at the time of slit coating can be prevented, leveling can be exhibited after coating, and coating unevenness, coating stripes, etc. can be prevented. . Further, in the ink jet system, it is possible to prevent the nozzle from being dried and promote the flattening of the liquid after droplet ejection.

Examples of the solvent having a boiling point at normal pressure of 160 ° C. or higher and lower than 190 ° C. include the following, but the present invention is not limited thereto.
Ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 2-ethoxypropionate, isoamyl propionate, cyclohexyl acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, propylene glycol phenyl ether acetate, propylene glycol butyl ether, propylene glycol propyl Examples include ether acetate, 3-methoxy-3-methylbutyl acetate, and the like. Among them, ethyl 3-ethoxypropionate (boiling point: 170 ° C.), cyclohexyl acetate (boiling point: 177 ° C.), 3-methoxybutyl acetate boiling point: 171 ° C. ) Is more preferable.
These solvents may be used alone or in combination of two or more.

As a preferable combination of the solvents used in the present invention, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone as a solvent having a boiling point of less than 160 ° C .; ethyl 3-ethoxypropionate as a solvent having a boiling point of 160 ° C. or more and less than 190 ° C., Cyclohexyl acetate and 3-methoxybutyl acetate.
Particularly preferred combinations of the solvents used in the present invention include propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether as solvents having a boiling point of less than 160 ° C .; ethyl 3-ethoxypropionate and cyclohexyl as solvents having a boiling point of from 160 ° C. to less than 190 ° C. Acetate.

  In the coloring composition, the content of the solvent (total amount including tetrahydrofurfuryl acetate) is 60 to 90% by mass, more preferably 70 to 90% by mass, and still more preferably 80 to 90% by mass. . By setting it in the above range, the film thickness uniformity is improved.

<Colorant>
The coloring composition of the present invention contains a colorant.
There is no restriction | limiting in particular in the coloring agent contained in the coloring composition of this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types. The colorant is preferably a pigment from the viewpoint of light resistance.

-Pigment-
As the pigment that can be used in the coloring composition of the present invention, various conventionally known inorganic pigments or organic pigments can be used. Also, considering that it is preferable that the pigment has a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible and a particle size as small as possible. Then, it is preferably a pigment having an average 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.

  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 4,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,

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, 58
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. Things, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28,
C. I. Pigment Black 1, 7 and the like.

  Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.

C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37, 58
C. I. Pigment Black 1, 7

These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of such combinations are shown below.
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 of an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, and 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. A mixture with CI Pigment Red 177 is preferred. Further, the mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80 in terms of color purity and coloring ability. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  Further, as the green pigment, one kind of halogenated phthalocyanine pigment or a mixture of this with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment is used. be able to. For example, C.I. I. Pigment green 7, 36, 37, 58 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. A mixture of CI Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200 from the viewpoints of color purity, color developing power, and NTSC target hue. 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: 70, more preferably 100: 50 or less.

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

In the present invention, a fine and sized organic pigment can be used as necessary.
In order to refine the organic pigment, it is preferable to use a method including a step of grinding the organic pigment as a highly viscous liquid composition together with the water-soluble organic solvent and the water-soluble inorganic salts.
In the present invention, it is more preferable to use the following method for refining the organic pigment.
That is, first, for a mixture (liquid composition) of an organic pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, a two-roll, a three-roll, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single The organic pigment in the mixture is ground by applying a strong shearing force using a kneader such as a twin or twin screw extruder, and then the mixture is put into water and made into a slurry with a stirrer or the like. Next, this slurry is filtered, washed with water, the water-soluble organic solvent and the water-soluble inorganic salt are removed, and then dried to obtain a refined organic pigment.

Examples of the water-soluble organic solvent used in the above-mentioned refinement method include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monoester. Examples include butyl ether, propylene glycol, and propylene glycolic monomethyl ether acetate.
Also, if it is adsorbed to the pigment by using a small amount and does not run away in 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. May be. Moreover, you may mix and use 2 or more types of solvents as needed.
The amount of these water-soluble organic solvents used is preferably in the range of 50% by mass to 300% by mass and more preferably in the range of 100% by mass to 200% by mass with respect to the organic pigment.

In the present invention, sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like are used as the water-soluble inorganic salt.
The amount of the water-soluble inorganic salt used is preferably 1 to 50 times the mass of the organic pigment, and a larger amount has a grinding effect, but from the viewpoint of productivity, a more preferred amount is 1 to 10 times the mass. is there.
In order to prevent dissolution of the water-soluble inorganic salt, the water content in the liquid composition to be ground is preferably 1% by mass or less.

In the present invention, when grinding a liquid composition containing an organic pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, a wet grinding device such as the above-mentioned kneader may be used. There are no particular restrictions on the operating conditions of this wet pulverizer, but the operating conditions when the apparatus is a kneader are used to rotate the blades in the apparatus in order to effectively proceed grinding with pulverizing media (water-soluble inorganic salt). The number is preferably 10 rpm to 200 rpm, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry pulverization time, and the internal temperature of the apparatus is preferably 50 ° C to 150 ° C. Further, the water-soluble inorganic salt that is a pulverizing medium preferably has a pulverized particle size of 5 μm to 50 μm, a sharp particle size distribution, and a spherical shape.
The mixture after milling as described above is mixed with warm water at 80 ° C. to dissolve the water-soluble organic solvent and the water-soluble inorganic salts, and then filtered, washed with water, dried in an oven, Organic pigments can be obtained.

-Dye-
In the present invention, when a dye is used as the colorant, it can be uniformly dissolved in the composition to obtain a curable composition.
The dye that can be used as the colorant contained in the coloring composition of the present invention is not particularly limited, and conventionally known dyes for color filters 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 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be suitably used from the viewpoint of completely removing the binder polymer and / or the dye in the non-irradiated part by development. .
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, and other components in the composition. It is selected in consideration of all required performance such as interaction with components, light resistance, heat resistance and the like.
Specific examples of the acid dye are shown below, but are not limited thereto.
For example, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83 , 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3 , 5, 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17 , 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.

Among these, acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, 63 , 74; acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; acid violet 7; acid yellow 17, 25, 29, 34 , 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; acidgreen 25 and the like and derivatives of these dyes are preferred.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Solvent orange 45; Rhodamine B, Rhodamine 110 and other acid dyes and derivatives of these dyes are also preferably used.

  Among them, as the colorant, triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazoleazo A colorant selected from anilinoazo, pyrazolotriazole azo, pyridone azo, and anthrapyridone is preferred.

The colorant that can be used in the present invention is a dye or a pigment having an average particle diameter r (unit: nm) satisfying 5 ≦ r ≦ 250, preferably 10 ≦ r ≦ 200, particularly preferably 15 ≦ r ≦ 150. desirable. By using a pigment having such an average particle diameter r, a colored pixel having a high contrast ratio and a high light transmittance can be obtained. The “average particle diameter” as used herein means the average particle diameter of secondary particles in which primary particles (single microcrystals) of the pigment are aggregated.
In addition, the particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of the secondary particles falling within (average particle size ± 100) nm. As mentioned above, it is desirable that it is 80 mass% or more.

  The pigment having the above average particle size and particle size distribution is preferably a commercially available pigment mixed with other pigments optionally used (average particle size usually exceeds 300 nm), preferably with a dispersant and a solvent. The pigment mixture liquid prepared can be prepared, for example, by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

-Pigment dispersion-
The pigment dispersion containing the above pigment is obtained by dispersing a pigment as a colorant in a solvent together with a dispersant and a pigment derivative.
The dispersant used here is used for improving the dispersibility of the pigment. For example, a known pigment dispersant or surfactant can be appropriately selected and used.
Hereinafter, the dispersant will be described.

<Dispersant>
Specifically, many types of compounds can be used as the dispersant. For example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants (manufactured by Nippon Lubrizol Co., Ltd.) such as 26000, 28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 62,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (BYK Chemie Co., Ltd.) and the like. In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, may be mentioned.

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

In addition, a pigment derivative is added to the pigment dispersion in the present invention as necessary.
In the present invention, a part having affinity with the dispersant or a pigment derivative having a polar group introduced is adsorbed on the surface of the pigment, and this is used as an adsorption point of the dispersant, whereby the pigment is dispersed as fine particles. It can be dispersed in the liquid, and re-aggregation can be prevented. That is, the pigment derivative has an effect of promoting the adsorption of the dispersant by modifying the pigment surface.

  Specifically, the pigment derivative used in the present invention 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 as a substituent in the side chain. Specific examples of organic pigments serving as a base skeleton include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzoic pigments. Examples include imidazolone pigments. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included.

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

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

Examples of the solvent constituting the pigment dispersion in the present invention include the same solvents as those described above.
The pigment concentration in the pigment dispersion is preferably 5% by mass to 60% by mass, more preferably 5% by mass to 80% by mass, and still more preferably 10% by mass to 30% by mass.
When the concentration of the colorant is within the above range, the color density is sufficient to ensure excellent color characteristics.
In the present invention, when a pigment derivative is used, the pigment concentration of the curable coloring composition in 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 curable coloring composition. Is used.

The pigment dispersion in the present invention can be prepared through a mixing and dispersing step of mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

Specifically, for example, a bead disperser using zirconia beads or the like (for example, manufactured by GETZMANN Co., Ltd.) is prepared by previously mixing a pigment and a dispersant as necessary, and further dispersing in advance with a homogenizer or the like. The pigment dispersion liquid can be prepared by finely dispersing using a disperse mat).
The dispersion time is preferably about 3 to 6 hours.
The fine dispersion treatment with beads mainly includes vertical or horizontal sand grinders, pin mills, slit mills, ultrasonic dispersers, etc., and beads made of glass having a particle diameter of 0.01 to 1 mm, zirconia, etc. Can be used.
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.

The colored composition of the present invention has excellent suitability for use, in particular, non-aggregation, non-crystallinity, fluidity, and excellent coloring power. Therefore, the coloring composition has paints, various inks such as printing inks and inkjet inks. The present invention is suitably used for the formation of multicolored images on a substrate such as a color display panel or a color proof, particularly for the production of color filters used in liquid crystal color displays, solid-state imaging devices and the like.
When a coating film is formed using the colored composition of the present invention, it becomes easy to control the drying property of the coating film, and it is possible to form a coating film having high coating thickness uniformity without coating unevenness. is there. Moreover, since the coloring composition of this invention is excellent in the dispersibility of a coloring agent, it is suitable for dispersion | distribution of a fine pigment. Therefore, by using the coloring composition, it is possible to provide a color filter and a liquid crystal display device with high luminance and high contrast.

[Curable coloring composition]
The curable coloring composition of the present invention further includes a polymerizable compound, a polymerization initiator, and a resin in addition to the coloring composition of the present invention containing the aforementioned colorant, a dispersant, and a solvent containing tetrahydrofurfuryl acetate. Containing.
Hereinafter, each component will be described.

<Polymerizable compound>
As the polymerizable compound that can be used in the present invention, a compound widely known as a compound having an ethylenically unsaturated double bond in the industrial field can be used without any particular limitation. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, etc. . Moreover, the EO modified body of these compounds, or PO modified body is also mentioned.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and their EO-modified product, PO-modified products thereof.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (E) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (E)
(However, R ⁴ and R ⁵ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a curable composition having a very high photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  In the present invention, when a polymerizable compound is added, it preferably contains two or more ethylenically unsaturated bonds, and more preferably contains three or more from the viewpoint of curing sensitivity. Especially, it is preferable to contain 2 or more (meth) acrylic acid ester structures, it is more preferable to contain 3 or more, and it is most preferable to contain 4 or more. Furthermore, it is preferable to contain an EO modified body from the viewpoint of curing sensitivity and developability of the unexposed area. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Made), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha).

  Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, Dipentaerythritol hexaacrylate EO modified products such as DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 are commercially available products. (Manufactured by Kyoeisha) is more preferred.

It is preferable that content of the polymeric compound in the curable coloring composition of this invention is 1-90 mass% with respect to the total solid of a curable coloring composition, and it is 5-80 mass%. More preferably, it is more preferably 10% to 70% by mass.
In particular, when the curable coloring composition of the present invention is used for the formation of a colored pattern of a color filter, the content of the polymerizable compound is such that the photosensitivity, support adhesion, and degree of curing are further improved. It is preferable that it is 5-50 mass% with respect to the total solid of the curable coloring composition of invention, It is more preferable that it is 7-40 mass%, It is still more preferable that it is 10-35 mass%.

<Polymerization initiator>
The curable coloring composition of the present invention contains a polymerization initiator.
The polymerization initiator used in the curable coloring composition of the present invention is not particularly limited as long as it can be decomposed by the application of energy such as radiation, light irradiation, and heating to generate an initial species. A polymerization initiator etc. are mentioned preferably.
Examples of the polymerization initiator include halomethyloxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Active 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 No. 88050A, benzophenones described in US Pat. No. 4,199,420, etc. Aromatic ketone compounds, (thio) xanthone-based or acridine-based compounds described in French Patent 2,456,741, and biimidazole-based compounds including coumarin-based or lophine dimers described in JP-A-10-62986 , JP-A-8-015521, etc. Boron complex, etc., etc. can be mentioned.

  As polymerization initiators, (1) acetophenone series, (2) ketal series, (3) benzophenone series, (4) benzoin series / benzoyl series, (5) xanthone series, (6) active halogen compounds [(6-1 ) Triazine series, (6-2) halomethyloxadiazole series, (6-3) coumarin series], (7) acridine series, (8) biimidazole series, (9) oxime ester series, etc. Agents are preferred.

  (1) As the acetophenone photopolymerization initiator, for example, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylamino Acetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone 1,2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, etc. are preferred Can be listed.

  (2) Preferred examples of the ketal photopolymerization initiator include benzyldimethyl ketal and benzyl-β-methoxyethyl acetal.

  (3) Examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and 1-hydroxy. -Cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like can be preferably exemplified.

  (4) 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.

  (5) Preferred examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  (6) Examples of (6-1) triazine photopolymerization initiators that are active halogen compounds 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-dimethoxystyryl-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- A triazine etc. can be mentioned suitably.

(6-2) Examples of the halomethyloxadiazole photopolymerization initiator include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl). -1,3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl- Preferable examples include 1,3,4-oxodiazole.
Examples of (6-3) coumarin-based photopolymerization initiators include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin and 3-chloro-5-diethylamino. Preferred examples include-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like. be able to.

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

  (8) Examples of biimidazole photopolymerization initiators known as lophine dimers include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5. Preferred examples include -diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide, and the like. be able to.

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

In the present invention, the polymerization initiator is not limited to the above, and other known initiators 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, a 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 JP-A 2000-66385.
Moreover, these polymerization initiators can also be used in combination.

  As content in the curable coloring composition of a polymerization initiator, 0.1 mass%-15.0 mass% are preferable with respect to the total solid of this composition, More preferably, 0.5 mass%- It is 12.0 mass%, More preferably, it is 1.0 mass%-10.0 mass%. When the content of the polymerization initiator is within the above range, the polymerization reaction can be favorably progressed to form a film with good strength.

<Resin>
The curable coloring composition of the present invention contains a resin.
The resin is a linear organic high molecular polymer, and at least one group that promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain) ( For example, it can be appropriately selected from alkali-soluble resins having a carboxyl group, a phosphoric acid group, a sulfonic acid group, and the like. Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For production of the alkali-soluble resin, for example, a known radical polymerization method can be applied. 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, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Preferred examples also include acidic cellulose derivatives having a carboxylic acid, and polymers having a hydroxyl group and an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
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.

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 acrylate, tolyl acrylate, naphthyl acrylate, and cyclohexyl acrylate.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. = CR ¹ R ² , CH ² = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² represents an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. And the like.

These other copolymerizable monomers can be used singly or in combination of two or more. Preferred other copolymerizable monomers are selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH ₂ ═CR ¹ R ² and / or CH ₂ ═C (R ¹ ) (COOR ³ ).

  As content of resin in a curable coloring composition, 1-40 mass% is preferable with respect to the total solid of this composition, More preferably, it is 2-30 mass%, More preferably, it is 3 ˜20 mass%.

<Other ingredients>
In the curable coloring composition of the present invention, if necessary, a sensitizing dye, a hydrogen-donating compound, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, the above-mentioned Various additives such as a polymer compound other than the alkali-soluble resin (binder polymer), a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

-Sensitizing dye-
A sensitizing dye may be added to the curable coloring composition of the present invention as necessary. The sensitizing dye can accelerate the radical generating reaction of the photopolymerization initiator and the polymerization reaction of the photopolymerizable compound by the exposure at a wavelength that can be absorbed by the sensitizing dye.
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; dyes described in JP-A-57-1605; 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 non-metal atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. Also good. W represents an oxygen atom or a sulfur atom.
Preferred specific examples [(F-1) to (F-5)] of the compound represented by the general formula (XIV) are shown below.

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

In the general formula (XVI), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic 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 or a substituted or unsubstituted aryl group, and L ⁵ And L ⁶ each independently represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ , A ⁴ and adjacent carbon atoms, and R ⁶¹ and R ⁶² each independently represent one group. It can be a valence non-metallic atomic group or 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, a sulfur atom, or —N (R ¹ ) —, and Y represents an oxygen atom or -N (R < ¹ >)-is represented. R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ¹ , R ² and R ³ are bonded to each other to form an aliphatic group Or an aromatic ring can be formed.

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

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

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

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and 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 and 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, and among these, a phenyl group and a naphthyl group are more preferable. .

Specific examples of the substituted aryl group that is preferable as R ¹ , R ² , and R ³ include a monovalent non-metallic atomic group (other than a hydrogen atom) as a substituent on the ring-forming carbon atom of the aforementioned aryl group. What you have 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. Further, more preferred examples of R ¹ include a substituted or unsubstituted aryl group. The reason is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical, acid or base of the initiator compound is generated. It is estimated that the efficiency is improved.

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

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

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

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

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

  Of the examples of the nitrogen-containing or sulfur-containing heterocycle formed by Y in cooperation with the above-mentioned A and the adjacent carbon atom in the general formula (XVIII) described above, the partial structure of the following general formula (XVIII-2) The dye having the structure represented by the formula is particularly preferable because it provides a photosensitive composition having high sensitizing ability and extremely excellent storage stability. The dye having the structure represented by the general formula (XVIII-2) is a compound described in detail in Japanese Patent Application No. 2003-31253 as a novel compound.

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

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

In the general formula (XVIII-3), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom, 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) Is synonymous with.
Ar in the general formula (XVIII-3) represents an aromatic ring or a hetero ring having a substituent, and as specific examples, among those described above in the description of A in the general formula (XVIII), Specific examples relating to the aromatic ring or heterocyclic ring having a substituent are also included. 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 (For example, —SOCH ₃ , m: 0.52, p: 0.45), an amide group (for example, —NHCOCH ₃ , m: 0.21, p: 0.00), a carboxyl group (—COOH, m: 0. 37, p: 0.45). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is. Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

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

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

  With respect to the sensitizing dye, various chemical modifications as described below can be performed for the purpose of improving the characteristics of the curable coloring 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, An improvement in the effect of suppressing the unnecessary precipitation of the dye from the crosslinked cured film can be obtained.

The content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, and still more preferably 0.1% with respect to the total solid content of the curable coloring composition. ˜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 curable coloring 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 the photopolymerization initiator to actinic radiation, or suppressing the polymerization inhibition of the polymerizable compound by oxygen.
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. No. 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.

  Other examples of the hydrogen donating compound include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, and JP-A-5-142277, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Further examples of the hydrogen donating compound include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B-55. -34414, a hydrogen donor described in JP-A-6-308727, and a sulfur compound (eg, trithiane).

  The content of these hydrogen-donating compounds ranges from 0.1 to 30% by mass with respect to the mass of the total solid content of the curable coloring composition from the viewpoint of improving the curing rate due to the balance between the polymerization growth rate and chain transfer. Is preferable, the range of 1-25 mass% is more preferable, and the range of 0.5-20 mass% is still more preferable.

-Fluorine organic compounds-
The curable coloring composition of the present invention can also contain a fluorine-based organic compound.
By containing this fluorinated organic compound, the liquid properties (particularly fluidity) when the curable coloring composition of the present invention is used as a coating liquid can be improved, and the uniformity of coating thickness and liquid-saving properties can be improved. Can be improved. That is, since the interfacial tension between the surface to be coated and the coating liquid is reduced, the wettability to the surface to be coated is improved, and the coating property to the surface to be coated is improved. Even when a thin film is formed, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  3-40 mass% is suitable for the fluorine content rate in a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 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.

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

  As described above, the fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness when the coating film is thinned. Furthermore, it is also effective when applied to slit coating that easily causes liquid breakage.

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

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

  The cresol novolac type includes Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above, manufactured by Tohto Kasei), Denacol EM-125, etc. (above, manufactured by Nagase Kasei), Biphenyl type As alicyclic epoxy compounds, such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl, Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302 , GT-401, GT-403, EHPE-3150 (manufactured by Daicel Chemical Industries), 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 In addition to diglycidyl ester, amine-type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl ester in which dimer acid is modified in the skeleton of bisphenol A-type epoxy resin can be used.

-Surfactant-
The curable coloring composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coatability, and various nonionic, cationic, and anionic surfactants can be used. Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.
Specific examples of the fluorosurfactant include Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and Fluorard (registered trademark) series manufactured by 3M.

  Moreover, a phthalocyanine derivative (commercial product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, poly Oxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Paluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, manufactured by BASF Nonionic surfactants such as 150R1 and anionic surfactants such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) can also be used.

-Other additives-
In addition to the above, as specific examples of additives, fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, Alkali-soluble resins such as those obtained by adding an acid anhydride to a polymer having a hydroxyl group, alcohol-soluble nylon, phenoxy resin formed from bisphenol A and epichlorohydrin; EFKA-46, EFKA-47, EFKA-47EA, EFKA High polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco) Molecular dispersant; Solsperse 3000 Various Solsperse dispersants such as 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, and 28000 (manufactured by Zeneca); , F77, P84, F87, P94, L101, P103, F108, L121, P-123 (above, manufactured by Asahi Denka Co., Ltd.), and Isonet S-20 (above, made by Sanyo Kasei); 2- (3-t- UV absorbers such as butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone; and aggregation inhibitors such as sodium polyacrylate.

In the case where the alkali solubility of the uncured part is promoted and the developability of the curable coloring composition is further improved, the curable coloring composition has an organic carboxylic acid, preferably a low molecular weight of 1000 or less. It is preferable to add an organic carboxylic acid.
Specific examples of the organic carboxylic acid include 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, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, etc. Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, Aromatic polymers such as terephthalic acid, trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid Rubonic acid; Phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylideneacetic acid, coumaric acid, and umberic acid Examples include acids.

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

(Preparation of curable coloring composition)
When the colorant is a pigment, first, after preparing a pigment dispersion as described above, the curable coloring composition of the present invention may be obtained using this pigment dispersion.
When the pigment dispersion is used for the preparation of the curable coloring composition of the present invention, the content thereof is 30% by mass or more and 60% by mass with respect to the total solid content (mass) of the curable coloring composition. An amount that is in the range of mass% or less is preferable, an amount in which the pigment content is in the range of 35 mass% to 60 mass% is more preferable, and a pigment content is in the range of 40 mass% to 60 mass%. A more preferred amount.
When the content of the pigment dispersion is within this range, the color density is sufficient and effective in securing excellent color characteristics.

<Color filter and manufacturing method thereof>

The color filter of the present invention is characterized in that it has a colored pattern formed on the substrate by the above-described curable coloring composition of the present invention.
Moreover, the manufacturing method of the color filter of this invention uses the above-mentioned curable coloring composition of this invention, and forms arbitrary colored patterns by repeating application | coating, prebaking, exposure, and image development.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

As described above, the method for producing a color filter of the present invention includes the steps of coating, pre-baking, exposure, and development. By passing through these steps, a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained.
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
Hereinafter, each step will be described in detail.

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

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

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

When forming a coating film with the curable coloring 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 μm. 0.0 μm, most preferably 0.5 to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking treatment) is preferably in the range of 0.5 to 5.0 μm.

In the coating process, usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking.
The vacuum drying condition is that the degree of vacuum is usually about 0.1 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. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. The high frequency treatment can be used alone.

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

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

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

The development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. Before the developer is touched, the surface to be developed can be previously moistened with water or the like to prevent uneven development. It is also possible to develop with the substrate tilted.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development processing, the substrate is dried through a rinsing process for washing and removing excess developer.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning. You may use the method of using ultrasonic irradiation together.

After drying as described above, heat treatment at 100 ° C. to 250 ° C. is usually performed.
In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.
Such post-baking is a process for the purpose of complete curing and for the purpose of forward-tapering the pattern shape after development by thermal deformation, and heating (hard baking) at 200 ° C. to 250 ° C. It is common to do.
Since the curable coloring composition of the present invention has a good cross-sectional shape and can form a film with high hardness, it has sufficient hardness and cross-sectional shape as a color filter after rinsing and drying. The post-baking in the color filter manufacturing process can be omitted.

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

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

<Liquid crystal display device>
The liquid crystal display element of the present invention comprises the color filter of the present invention.
More specifically, an alignment film is formed on the inner surface side of the color filter of the present invention, is opposed to the electrode substrate, and the gap is filled with liquid crystal and sealed to obtain a panel which is the liquid crystal display device of the present invention. It is done.

  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.

( Reference Example 1)
Phthalocyanine blue pigment C.I. I. 200 parts of Pigment Blue 15: 6, 2000 parts of sodium chloride, and 400 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 6 hours. Next, the kneaded product is poured into 20 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.
With the following composition 1, the mixture was stirred for 3 hours at a rotation speed of 3,000 rpm using a homogenizer to prepare a mixed solution.

[Composition 1]
Pigment Blue 15: 6 (average primary particle size 30 nm) 150 parts phthalocyanine derivative 10 parts (Solsperse 5000, manufactured by Nihon Lubrizol)
・ 75 parts of propylene glycol monomethyl ether acetate solution (solid content 40%) of benzyl methacrylate / methyl methacrylate (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 30,000) ・ Dispersant (BYK-161) 60 parts) Tetrahydrofurfuryl acetate 200 parts Propylene glycol monomethyl ether acetate 355 parts Ethyl 3-ethoxypropionate 150 parts

  Subsequently, the mixed solution (composition 1) 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 colored composition. Obtained.

( Reference Examples 2 to 13)
As shown in Table 1, solvent type, content, except for changing the pigment species in the same manner as in Reference Example 1 to obtain a wearing colored composition.

(Comparative Examples 1 to 10)
As shown in Table 1 below, a comparative colored composition was obtained in the same manner as in Reference Example 1 except that the solvent type, content, and pigment type were changed.

(Example 14)
The component of the following composition 2 was further added to the colored composition obtained in Reference Example 1, and the mixture was stirred and mixed to prepare the curable colored composition (color resist solution) of the present invention.

[Composition 2]
Dipentaerythritol pentahexaacrylate (polymerizable compound) 50 parts 4- [o-bromo-pN, N-di (ethoxycarbonyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine (Photopolymerization initiator) 5 parts-A solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 6,000) in propylene glycol monomethyl ether acetate (solid content 40%) ( Resin) 200 parts ・ Propylene glycol monomethyl ether acetate 745 parts

(Examples 15 to 24)
As shown in Table 2 below, a curable coloring composition (color resist solution) of the present invention was prepared in the same manner as in Example 14 except that the solvent type, solvent ratio, and pigment type were changed.

(Comparative Examples 11-17)
As shown in Table 2 below, a comparative curable coloring composition (color resist solution) was prepared in the same manner as in Example 14 except that the solvent type, content, and pigment type were changed.

(Production and measurement of measurement substrate, evaluation method)
-1. Evaluation of nozzle adhesion of aggregates
For each of the colored composition and the curable colored composition (color resist solution) prepared in each example , each reference example, and each comparative example, SHOTMASTER3 (a needle having an inner diameter of 0.17 mm at the tip of the syringe (Musashi) Using an engineering company, SN-28G) was used to observe and evaluate the deposit on the needle tip after drawing 100 mm in length 100 times.
Evaluation was made with “X” indicating that there was a deposit on the needle tip, and “◯” indicating that there was no deposit on the needle tip. The results are shown in Tables 1 and 2.

-2. Preparation of coated substrate and measurement of coating film thickness
Each of the coloring composition and the curable coloring composition (color resist solution) prepared in each Example , each Reference Example and each Comparative Example was placed on a different glass substrate (1737, manufactured by Corning) on a different 550 mm × 650 mm. The film was applied to a thickness of 0.0 μm and dried in an oven at 90 ° C. for 60 seconds (pre-baking). The film thickness was measured using DEKTAK (manufactured by ULVAC).
Film thickness uniformity: The rate obtained by dividing the maximum film thickness or the minimum film thickness by the average film thickness at 50 locations was evaluated as ◯ when less than 3%, Δ when 3% or more and less than 6%, and × when 6% or more. The results are shown in Tables 1 and 2.

-3. Measurement and evaluation of luminance (Y value) and contrast
The Y value and contrast of the coated substrate produced as follows were measured. The results are shown in Tables 1 and 2.
(A) Y value About each of the produced coated substrate, Y value was measured using MCPD-2000 made from Otsuka Electronics. The Y value indicates that the luminance is higher as the value is larger.
(B) Contrast A polarizing plate is placed on the colored coating film of the prepared coated substrate, and the colored coating film is sandwiched between them. The luminance when the polarizing plate is parallel and the luminance when the polarizing plate is orthogonal are BM-5 manufactured by Topcon Corporation. The value obtained by dividing the parallel brightness by the orthogonal brightness (= the parallel brightness / the orthogonal brightness) was used as an index for evaluating the contrast.
Y value: A value 0.5 or higher than the comparative example using the same pigment type was evaluated as ◯, and a value less than 0.5 was evaluated as x.
Contrast: Evaluation was made with a value higher by 1.2 times or more than that of the comparative example using the same pigment type as ◯ and a value lower than 1.2 times as x.

Abbreviations in Table 1 and Table 2 are as follows.
THFFA: tetrahydrofurfuryl acetic acid PGMEA: propylene glycol monomethyl ether acetate EEP: ethyl 3-ethoxypropionate CHXA: cyclohexyl acetate MFG: propylene glycol monomethyl ether MBA: 3-methoxybutyl acetate PB15: 6: Pigment Blue 15: 6
PV23: Pigment Violet 23
PG36: Pigment Green 36
PY150: Pigment Yellow 150
PR254: Pigment Red 254
PR177: Pigment Red 177

It can be seen that the coloring compositions of Reference Examples 1 to 13 and the curable coloring compositions of Examples 14 to 24 are excellent in dispersibility and film thickness uniformity because aggregation is suppressed. Further, when the composition is used for a color filter, it can be seen that it has high luminance and high contrast.

Claims (6)

A curable coloring composition containing a colorant, a dispersant, a solvent, a polymerizable compound, a polymerization initiator, and a resin, and containing 1 to 50% by mass of tetrahydrofurfuryl acetate. . 2. The curable coloring composition according to claim 1, wherein the solvent contains 20 to 80% by mass of a solvent having a boiling point of less than 160 ° C. at normal pressure in the total amount of the solvent. 3. The curable coloring composition according to claim 1, wherein 10 to 40% by mass of a solvent having a boiling point at normal pressure of 160 ° C. or more and less than 190 ° C. is contained in the total amount of the solvent. The curable coloring composition according to claim 1, wherein the resin is an alkali-soluble resin. A color filter comprising a colored layer produced using the curable coloring composition according to any one of claims 1 to 4 . A liquid crystal display device comprising the color filter according to claim 5 .