JP2013210525A - Colored curable composition and manufacturing method thereof, color filter and manufacturing method thereof, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable composition capable of forming a colored cured film hardly causing reduction in brightness due to heating during a step and having high brightness; a color filter allowing display of an image with brightness and high contrast and a manufacturing method thereof; and a display device with good image quality.SOLUTION: The colored curable composition of the present invention comprises: an organic pigment; a dye comprising a mother skeleton different from the organic pigment and being adsorbed to the surface of the organic pigment; and an alkali-soluble resin comprising a structural unit (b1) having a carboxyl group on the side chain and a structural unit (b2) where at least one kind compound selected from compounds represented by the general formula (i) and compounds represented by the general formula (ii) is added to the structural unit (b1). In the general formula (i) and the general formula (ii), Z represents a hydrogen atom or a methyl group.

Description

  The present invention relates to a colored curable composition and a method for producing the same, a color filter produced using the colored curable composition, a method for producing the same, and a display device including the color filter.

  A pigment dispersion method is widely used as one of methods for producing a color filter used for a liquid crystal display device, a solid-state imaging device, or the like. As a pigment dispersion method, there is a method of producing a color filter by a photolithography method using a colored curable composition in which a pigment is dispersed in various photosensitive compositions. Since this method performs patterning by a photolithographic method, it is considered to be a method suitable for manufacturing a color filter with high positional accuracy and a large screen.

  In order to produce a color filter by the pigment dispersion method, first, a colored curable composition is applied onto a substrate with a spin coater, a roll coater, or the like, and dried to form a coating film. Next, the coating film is exposed and developed to form a colored pattern. A color filter can be produced by repeating this operation for each color. As a colored curable composition used for producing a color filter, for example, one containing a phthalocyanine pigment is known (for example, see Patent Document 1).

  By the way, in recent years, the demand for the performance of the color filter has been increasing, and in particular, the hue and the luminance are emphasized. Under such circumstances, a technique using a dye as a colored compound instead of a pigment has been proposed (see, for example, Patent Documents 2 to 4). Dyes are useful in that the hue and brightness of a display image can be increased when an image is displayed due to the color purity and hue vividness of the dye.

JP 2001-33616 A Japanese Patent No. 3387541 JP 2008-292970 A JP 2009-86375 A

  However, color filters using dyes are generally known to be inferior in heat resistance compared to pigments, and further improvements are required for their use in order to fully demonstrate the performance of dyes. ing.

The present invention has been made in view of the above circumstances, and provides a colored curable composition that can hardly form a reduced luminance due to heating during the process and that can form a colored cured film with high luminance, and a method for producing the same. The task is to do.
Another object of the present invention is to provide a color filter capable of displaying a high-brightness and high-contrast image, a method for manufacturing the same, and a display device with good image quality.

  Specific means for achieving the above object are as follows.

  (1) an organic pigment, a structural unit (b1) having a mother skeleton different from the organic pigment, adsorbed on the surface of the organic pigment, a carboxyl group in the side chain, and the structural unit (b1) And a structural unit (b2) obtained by adding at least one compound selected from the compound represented by the following general formula (ii) and at least one compound selected from the following general formula (ii) to at least a part of And a colored curable composition comprising a polymerizable compound.

  In general formula (i) and general formula (ii), Z represents a hydrogen atom or a methyl group.

  (2) The colored photosensitive composition according to (1), wherein the alkali-soluble resin further includes a structural unit (b3) having a polycyclic alicyclic alkyl group in a side chain.

  (3) The colored photosensitive composition according to (2), wherein the polycyclic alicyclic alkyl group is a tricyclodecanyl group or a dicyclopentadienyl group.

  (4) The colored photosensitive resin according to any one of (1) to (3), wherein the content of the structural unit (b2) is 0.1% by mass or more and 70% by mass or less in the alkali-soluble resin. Composition.

  (5) The coloring according to any one of (1) to (4), wherein the content of the alkali-soluble resin is 1% by mass to 70% by mass with respect to the total solid content of the colored photosensitive composition. Photosensitive composition.

  (6) The colored curable composition according to any one of (1) to (5), wherein the organic pigment is a phthalocyanine pigment.

  (7) The colored curable composition according to any one of (1) to (6), wherein the dye is a complex in which a compound represented by the following general formula (I) is coordinated to a metal atom or a metal compound. object.

(In general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ is a hydrogen atom, Represents a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.)

  (8) The colored curable composition according to any one of (1) to (7), further comprising a photopolymerization initiator.

  (9) At least an organic pigment, a dye containing a mother skeleton different from the organic pigment, adsorbed on the surface of the organic pigment, a structural unit (b1) having a carboxyl group in a side chain, and the structural unit (b1) And a structural unit (b2) obtained by adding at least one compound selected from the compound represented by the following general formula (ii) and at least one compound selected from the following general formula (ii) to at least a part of A method for producing a colored curable composition comprising mixing a polymerizable compound and a solvent through a process of dispersing the organic pigment in the solvent in the presence of at least the dye.

  In general formula (i) and general formula (ii), Z represents a hydrogen atom or a methyl group.

  (10) The colored curable composition according to (9), wherein the process comprises kneading at least the organic pigment and the dye together with a solvent, and further mixing the obtained kneaded material with a solvent to disperse the organic pigment. A method for producing the composition.

  (11) The colored curable composition according to any one of (1) to (8) or the colored curable composition obtained by the production method according to (9) or (10). Color filter.

  (12) The colored curable composition according to any one of (1) to (8) or the colored curable composition obtained by the production method according to (9) or (10) A colored layer forming step of forming a colored layer by applying to the substrate, an exposure step of exposing the formed colored layer in a pattern manner, and a developing step of developing the colored layer after exposure to form a colored pattern A method for producing a color filter.

  (13) A display device comprising the color filter according to (11) or the color filter obtained by the production method according to (12).

  (14) The colored curable composition according to any one of (1) to (8) or (9) or (10) on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. A liquid crystal display device comprising a color filter having pixels formed of a colored curable composition obtained by the manufacturing method of

According to the present invention, it is possible to provide a colored curable composition that can hardly form a reduced luminance due to heating during the process and that can form a colored cured film with high luminance, and a method for producing the same.
Furthermore, according to the present invention, it is possible to provide a color filter capable of displaying an image with high brightness and high contrast, a method for manufacturing the same, and a display device with good image quality.

It is the schematic of the main electrode and guard electrode which were produced in the measurement of a dielectric constant.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

The colored curable composition of the present invention includes an organic pigment, a dye containing a mother skeleton different from the organic pigment, adsorbed on the surface of the organic pigment, and a structural unit (b1) having a carboxyl group in a side chain. And a structural unit (b2) obtained by adding at least one compound selected from a compound represented by the following general formula (i) and a compound represented by the general formula (ii) to at least a part of the structural unit (b1): ), An alkali-soluble resin (hereinafter sometimes referred to as “specific alkali-soluble resin”), and a polymerizable compound.
In recent years, hue and brightness have become important in the performance of color filters, and instead of conventional pigments, dyes tend to be used as colorants. Dyes are useful in that the hue and brightness of a displayed image can be increased when an image is displayed due to the color purity and hue vividness of the dye, but in general, heat resistance is inferior to pigments. Therefore, hitherto, the performance of dyes has not been fully exhibited. The colored curable composition of the present invention includes an organic pigment, a dye containing a mother skeleton different from the organic pigment, a specific alkali-soluble resin, and a polymerizable compound, and further includes at least one of the above dyes. When the part is in a state of being adsorbed on the surface of the organic pigment, the heat resistance is increased, and the performance of improving the hue and brightness of the display image inherent to the dye can be sufficiently exerted. It is significant that the formation of a high-brightness colored cured film can be realized.

  Moreover, according to the colored curable composition of this invention, the colored cured film which has tolerance with respect to strong solvents, such as NMP (N-methyl-pyrrolidone), can also be formed. In general, a liquid crystal display device is manufactured by separately manufacturing a color filter substrate and a TFT (Thin-Film-Transistor) substrate and attaching them with a liquid crystal interposed therebetween. At this time, in the color filter substrate, an alignment film such as polyimide for aligning liquid crystal is formed on the color filter layer. Therefore, the colored cured film is required to have resistance to a solvent having a strong polarity such as NMP contained in the polyimide resin. However, according to the colored curable composition of the present invention, such a requirement can also be satisfied.

  Further, in a COA (Color-filter On Array) type liquid crystal display device, a color filter layer that also serves as an interlayer insulating film is formed on the TFT. Performance is also required. According to the colored curable composition of the present invention, it is possible to form a colored cured film having performance as an interlayer insulating film, such as low dielectric constant and peeling liquid resistance.

  Here, in the colored photosensitive composition of the present invention, the reason why the above effect is exerted is not clear, but the specific alkali-soluble resin is selected from the compounds represented by the general formula (i) and the general formula (ii). It is considered that the alkali-soluble resin is polymerized by exposure and heat to form a crosslinked structure due to the carbon-carbon unsaturated bond group of the group derived from at least one kind of compound in the side chain. It is.

[Colored curable composition]
The colored curable composition of the present invention comprises an organic pigment, a dye containing a mother skeleton different from the organic pigment, adsorbed on the surface of the organic pigment, a specific alkali-soluble resin, and a polymerizable compound. It is characterized by including, and it is preferable that a photoinitiator is further included.
The colored curable composition of the present invention comprises an organic pigment, a dye containing a mother skeleton different from the organic pigment, adsorbed on the surface of the organic pigment, a specific alkali-soluble resin, and a polymerizable compound. The others are not particularly limited, and may optionally contain a photopolymerization initiator, a binder, an organic solvent, and various additives as long as the effects of the present invention are not impaired.
Hereinafter, each component which comprises the colored curable composition of this invention is demonstrated in detail.

-Organic pigments-
The colored curable composition of the present invention contains at least one organic pigment. The organic pigment is not particularly limited, and various conventionally known organic pigments can be used.

In consideration of the production of a color filter having a high transmittance, it is preferable to select a pigment having a small particle size as small as possible. In particular, when the handling property is taken into consideration, the average primary particle diameter is preferably 10 nm to 30 nm, more preferably 10 nm to 15 nm. When the average primary particle diameter of the organic pigment is within the above range, a color filter having high transmittance, good color characteristics, and high contrast can be formed.
The average primary particle diameter is obtained by observing with an SEM or TEM, measuring the particle size of 100 particles where the particles are not aggregated, and calculating the average value.

As an organic pigment, for example,
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37,
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 were changed to OH. Stuff, 80,
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42,
C. I. Pigment Brown 25, 28,
C. I. Pigment Black 1, 7 and the like. However, the organic pigments in the present invention are not limited to these, and these organic pigments can be used alone or in various combinations in order to increase color purity.

As the organic pigment in the present invention, a blue pigment is preferable, and among them, a phthalocyanine pigment is more preferable from the viewpoint that the hue is good and the contrast of the cured film can be improved.
Examples of the phthalocyanine pigment include C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH 80, etc. Among these, C.I. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66 are preferable. I. Pigment Blue 15: 6 is preferable from the viewpoint of color reproducibility.

(Miniaturization of organic pigments)
As the organic pigment, if necessary, fine and sized particles can be used. To refine organic pigments, organic pigments are kneaded and dispersed together with water-soluble organic solvents and water-soluble inorganic salts to prepare a high-viscosity liquid composition. This is achieved through a refinement process of grinding.

Examples of the water-soluble organic solvent used in the organic pigment refining process include methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Examples include butyl ether, propylene glycol, propylene glycol monomethyl ether acetate and the like.
In addition, as long as it is adsorbed to the organic pigment by being used in a small amount and is not washed away in the wastewater, it is low in water solubility or other solvent having no water solubility, such as 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, methylcyclohexane, halogenated hydrocarbons, acetone, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, or the like may be used.
Only one type of solvent may be used in the step of refining the organic pigment, or two or more types may be mixed and used as necessary.

Examples of the water-soluble inorganic salt used in the organic pigment refinement step include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate and the like.
The amount of the water-soluble inorganic salt used in the refining step is 1 to 50 times by mass of the organic pigment, and a larger amount has a grinding effect, but a more preferable amount is 1 to 10 times by mass of the pigment in terms of productivity. It is. Moreover, it is preferable to use inorganic salts having a moisture content of 1% or less.
The usage-amount of the water-soluble organic solvent in a refinement | miniaturization process is the range of 50 mass parts-300 mass parts with respect to 100 mass parts of organic pigments, Preferably it is the range of 100 mass parts-200 mass parts.

  There are no particular restrictions on the operating conditions of the wet pulverization apparatus in the miniaturization process, but the operating conditions when the apparatus is a kneader are the rotational speed of the blade in the apparatus in order to effectively proceed the grinding with the pulverization media. The rotation speed is preferably 10 to 200 rpm, and a relatively large biaxial rotation ratio is preferable because the grinding effect is increased. The operation time is preferably 1 to 8 hours in combination with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Moreover, the water-soluble inorganic salt which is a pulverization medium preferably has a pulverization particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

  The content of the organic pigment in the colored curable composition of the present invention is preferably 0.5 to 50% by mass, and preferably 1 to 30% by mass with respect to the total solid content of the composition. More preferred. When the content of the organic pigment is within the above range, excellent color characteristics can be ensured.

  In addition, in the colored curable composition of this invention, a conventionally well-known various inorganic pigment may be included other than an organic pigment as a pigment. Examples of inorganic pigments 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, etc. And metal oxides of the above metals.

-Dye-
The colored curable composition of the present invention contains at least one dye. The dye contains a mother skeleton different from the organic pigment. Here, the “matrix” refers to a molecular structure (chromophore) necessary for a compound to exhibit color. The mother skeleton is a structural part (conjugated system) constituted by a continuous unsaturated bond in the dye compound. For example, aromatic,> C = C <,> C = O,> C = N-,> N = N <, -N = O, etc. are connected structural parts. Specifically, for example, organic pigments such as nacridon pigments, phthalocyanine pigments, and azo pigments serve as the mother skeleton.

  In the colored curable composition of the present invention, the dye is adsorbed on the surface of the organic pigment. Here, “adsorbed on the surface” means a state in which the dye is attached to the organic pigment by an intermolecular interaction such as an ionic interaction.

In the colored curable composition of the present invention, it is sufficient that at least a part of the dye is adsorbed on the surface of the organic pigment, but 15% by mass or more of the dye is adsorbed on the surface of the organic pigment. Is preferred. When the proportion of the dye adsorbed on the surface of the organic pigment (hereinafter referred to as dye adsorption rate) is 15% by mass or more, the heat resistance of the dye is further increased, and as a result, a colored cured film with higher brightness is obtained. Can be formed.
The dye adsorption rate is a value calculated based on the following formula.
The supernatant in the following formula is a supernatant obtained by centrifuging a solution containing a dye and an organic pigment at 50000 rpm using an ultracentrifuge, and the amount of the dye in the supernatant is: Measure by quantitative analysis by HPLC.
Dye adsorption rate (%) = [1− (Amount of dye in supernatant (g) / Prescription amount of dye in solution (g))] × 100

  In the colored curable composition of the present invention, the dye is not particularly limited as long as it contains a mother skeleton different from the organic pigment, and a conventionally known dye used for color filter use is used. it can. 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, Japanese Patent 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 8-15522, JP 8-29771, JP 8-146215, JP 11-343. 37, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 Examples thereof include dyes described in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  Preferred chemical structures of the dye include pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole Examples include azomethine series, xanthene series, phthalocyanine series, benzopyran series, and indigo series.

  The dye in the present invention is preferably a complex (dipyrromethene metal complex compound) in which a compound represented by the following general formula (I) is coordinated to a metal atom or a metal compound in terms of spectral characteristics and heat resistance.

In general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, halogen, An atom, an alkyl group, an aryl group, or a heterocyclic group is represented.

In the general formula (I), examples of the monovalent substituent represented by R ^{1 to} R ⁶ include a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), an alkyl group (preferably having a carbon number of 1 to 48, more preferably a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group and 1-adamantyl group), alkenyl group (preferably). Is an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as a vinyl group, an allyl group, or a 3-buten-1-yl group. An aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably a carbon group). A heterocyclic group having 1 to 32, more preferably 1 to 18 carbon atoms, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl Group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably C3-C38, more preferably C3-C18 silyl group, For example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydro Sil group, cyano group, nitro group, alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group) Groups, isopropoxy groups, t-butoxy groups, dodecyloxy groups, and cycloalkyloxy groups include, for example, cyclopentyloxy groups and cyclohexyloxy groups).

  An aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably an aryloxy group having 6 to 24 carbon atoms, such as phenoxy group and 1-naphthoxy group), a heterocyclic oxy group (preferably carbon 1 to 32, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy group and 2-tetrahydropyranyloxy group), silyloxy group (preferably). Is a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, and examples thereof include a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, and a diphenylmethylsilyloxy group), an acyloxy group (preferably). Is an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms. A xoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, , An ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, and a cycloalkyloxycarbonyloxy group include, for example, a cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group (preferably having a carbon number of 7 to 32, more preferably an aryloxycarbonyloxy group having 7 to 24 carbon atoms, such as a phenoxycarbonyloxy group, and a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably 1 carbon atom). ~ 24 Cal And a sulfamoyloxy group such as N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group). Group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include N, N-diethylsulfamoyloxy group and N-propylsulfamoyloxy group. ),

  An alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include a methylsulfonyloxy group, a hexadecylsulfonyloxy group, and a cyclohexylsulfonyloxy group. ), An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), an acyl group (preferably having a carbon number). 1 to 48, more preferably an acyl group having 1 to 24 carbon atoms, and examples thereof include a formyl group, an acetyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group, and a cyclohexanoyl group. (Preferably 2 to 48 carbon atoms, more preferably An alkoxycarbonyl group having 2 to 24 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, or a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group. ), An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyl group), a carbamoyl group (preferably A carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group N-propylcarbamoy Group, N- phenylcarbamoyl group, N- methyl-N- phenylcarbamoyl group, N, include alkoxy carbamoyl group to N- dicyclohexyl.),

  Amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group) Group, a cyclohexylamino group), an anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24, such as an anilino group and an N-methylanilino group), hetero. A cyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 4-pyridylamino group), a carbonamido group (preferably having 2 to 48 carbon atoms, More preferred are 2 to 24 carbonamido groups, for example, acetamido group, benzamido group, tetradecanamido group, piva Ylamide group, cyclohexaneamide group, etc.), ureido group (preferably ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido group, N, N-dimethylureido group, N-phenylureido group), an imide group (preferably an imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, such as an N-succinimide group and an N-phthalimide group). An alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, octadecyl Oxycarbonylamino group, cyclohexyloxycarbonyl group Roh group and the like.),

  An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonylamino group), a sulfonamide group (preferably a carbon A sulfonamide group having 1 to 48, more preferably 1 to 24 carbon atoms, includes, for example, a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group, and a cyclohexanesulfonamide group. ), A sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino group, N-ethyl- N-dodecylsulfamoylamino group). A zo group (preferably an azo group having 1 to 32 carbon atoms, more preferably an azo group having 1 to 24 carbon atoms, such as a phenylazo group or a 3-pyrazolylazo group), an alkylthio group (preferably having a carbon number of 1 to 48, more preferably an alkylthio group having 1 to 24 carbon atoms, such as a methylthio group, an ethylthio group, an octylthio group, and a cyclohexylthio group, and an arylthio group (preferably having 6 to 48 carbon atoms, more preferably An arylthio group having 6 to 24 carbon atoms, for example, a phenylthio group), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, Examples include 2-benzothiazolylthio group, 2-pyridylthio group, and 1-phenyltetrazolylthio group.), Alkyls A finyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a dodecanesulfinyl group), an arylsulfinyl group (preferably having 6 to 32 carbon atoms, An arylsulfinyl group having 6 to 24 carbon atoms is preferable, and examples thereof include a phenylsulfinyl group. An alkylsulfonyl group (preferably having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms). Yes, examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, an isopropylsulfonyl group, a 2-ethylhexylsulfonyl group, a hexadecylsulfonyl group, an octylsulfonyl group, and a cyclohexylsulfonyl group. D Group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group. ), A sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group). Group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms). A phosphonyl group, for example, a phenoxyphosphonyl group, an octyloxyphosphonyl group, and a phenylphosphonyl group), a phosphinoylamino group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms). Phosphinoylamino group such as diethoxyphosphinoylamino group, dioctyloxy Sufi alkanoylamino group.) Represents the.

  When the monovalent substituent described above is a further substitutable group, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.

In the general formula (I), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to each other to form 5, 6 or 7 members. The ring may be formed. In addition, as a ring formed, either a saturated ring or an unsaturated ring may be sufficient. Examples of the 5-membered, 6-membered, or 7-membered saturated ring or unsaturated ring include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
In addition, when the 5-membered, 6-membered, and 7-membered rings formed are further substitutable groups, they are substituted with any of the groups exemplified as the monovalent substituent in the general formula (I). When it is substituted with two or more substituents, these substituents may be the same or different.
R ¹ and R ⁶ preferably do not form a ring.
In the general formula (I), when R ⁷ is a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, these preferred ranges are the halogen atom, alkyl group, and R ^{1 to} R ⁶ described above. This is the same as the preferred range of the aryl group or heterocyclic group.

In the general formula (I), R ¹ and R ⁶ are each independently an alkylamino group, an arylamino group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group. Preferred are carbonamido group, ureido group, alkoxycarbonylamino group and sulfonamido group, more preferred are carbonamido group, ureido group, alkoxycarbonylamino group and sulfonamido group, and particularly preferred are carbonamido group and ureido group. .

In general formula (I), R ² and R ⁵ are each independently an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, A carbamoylsulfonyl group is preferable, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group are more preferable, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitrile group, An imide group and a carbamoylsulfonyl group are more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
In general formula (I), as R ³ and R ⁴ , among these, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferable, More preferred is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

In general formula (I), the alkyl group represented by R ³ and R ⁴ is preferably a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, more specifically. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, t-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and Benzyl group is mentioned, More preferably, it is a C1-C12 branched chain or cyclic substituted or unsubstituted alkyl group, More specifically, for example, an isopropyl group, a cyclopropyl group, i-butyl group , T-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and more preferably, a secondary or tertiary substituted or unsubstituted alkyl having 1 to 12 carbon atoms. And a, more specifically, for example, isopropyl, cyclopropyl, i- butyl, t- butyl group, a cyclobutyl group, a cyclohexyl group.

In the general formula (I), the aryl group represented by R ³ and R ⁴ is preferably a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, more preferably a substituted or unsubstituted phenyl group. It is a group.
When R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group is preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, a substituted or unsubstituted 3 -Pyridyl group, substituted or unsubstituted 2-pyridyl group, substituted or unsubstituted 2-furyl group, substituted or unsubstituted 2-pyrimidinyl group, substituted or unsubstituted 2-benzothiazolyl group, substituted or unsubstituted 1 -Imidazolyl group, substituted or unsubstituted 1-pyrazolyl group, substituted or unsubstituted benzotriazol-1-yl group, more preferably substituted or unsubstituted 2-thienyl group, substituted or unsubstituted 4- Examples include a pyridyl group, a substituted or unsubstituted 2-furyl group, a substituted or unsubstituted 2-pyrimidinyl group, and a substituted or unsubstituted 1-pyridyl group.

Next, the metal atom or metal compound that forms the dipyrromethene metal complex compound will be described.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or 2 Valent metal chlorides are included. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl, InCl, FeCl, TiCl ₂ , SnCl ₂ , SiCl ₂ Further, metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO is most preferable. Among these, Zn is particularly preferable.

In the metal complex compound in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound, preferred embodiments are shown below.
That is, in general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy Group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone Represented by an amide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, wherein R ² and R ⁵ are each independently a hydrogen atom, a halogen atom, Atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxy Sil group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group , An alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, Aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamido group, ureido group, imide group An alkoxycarbonylamino group, Ruhon'amido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, represented by a sulfamoyl group, or a phosphinoylamino group, R ⁷ is a hydrogen atom, a halogen atom, an alkyl group , An aryl group, or a heterocyclic group, and the metal atom or metal compound is represented by Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO Is mentioned.

The more preferable aspect of a dipyrromethene metal complex compound is shown below.
That is, in the general formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, Amino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group R ² and R ⁵ are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide Group, alkylsulfonyl group, arylsulfonyl group, or sulfa Represented by a moyl group, and R ³ and R ⁴ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, carbonamido group, It is represented by a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ⁷ is a hydrogen atom or a halogen atom. , An alkyl group, an aryl group, or a heterocyclic group, and a metal atom or metal compound is represented by Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO.

  Preferred embodiments of the dipyrromethene metal complex compound represented by the above general formula (I) include a compound represented by the following general formula (I-2), a compound represented by the general formula (I-3), and a general formula Examples thereof include compounds selected from compounds represented by (I-4).

In the above general formula (I-2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as R ¹ , R ² , R ³ , R ⁴ , Each of R ⁵ , R ⁶ and R ⁷ has the same meaning. Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, and X ² represents a group necessary for neutralizing the charge of Ma. X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with Ma.

In the general formula ^{(I-2), R 1} ~R 7 of the general formula (I) in a respectively ^R 1 to R ⁷ synonymous, preferred embodiment is also the same.
In the general formula (I-2), Ma represents a metal atom or a metal compound, and the metal atom in the above “dipyrromethene metal complex compound in which the compound represented by the general formula (I) is coordinated to the metal atom or metal compound”. Or it is synonymous with a metal compound, The preferable range is also the same.

X ¹ in the general formula (I-2) may be any group as long as it is a group capable of binding to Ma, such as water, alcohols (for example, methanol, ethanol, propanol) and the like, and “metal chelate” [1 ] Groups derived from the compounds described in Takeichi Sakaguchi and Keihei Ueno (1995 Nanedou), [2] (1996), [3] (1997), and the like. Among these, from the viewpoint of production suitability, groups derived from water, carboxylic acid compounds, alcohols, amine compounds, and amide compounds are preferable, and groups derived from water, carboxylic acid compounds, and amide compounds are more preferable.

X ² in the general formula (I-2) represents a group necessary for neutralizing the charge of Ma. For example, a halogen atom, a hydroxyl group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, R—CONHCO—R (R is each independently an alkyl group, aryl group, heterocyclic group), R-CONHSO ₂ -R (R is each independently an alkyl group, aryl group, heterocyclic group), etc. In terms of production, a halogen atom, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, R—CONHCO—R, and R—CONHSO ₂ —R are preferable, and a hydroxyl group, a carboxylic acid group, and R—CONHCO—R are more preferable. .

X ¹ and X ² in formula (I-2) may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with Ma. The 5-membered, 6-membered and 7-membered rings formed may be saturated or unsaturated. The 5-membered, 6-membered, and 7-membered rings are heterocycles having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, which may be composed of only carbon and hydrogen atoms. There may be.

In the general formula (I-3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are R ¹ , R ² , R ³ , R ⁴ , R ⁵ in the general formula (I). , And R ^{6 are as} defined above. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or a monovalent substituent. Ma represents a metal atom or a metal compound.

In the general formula ^{(I-3), R 1} ~R 6 of the general formula (I) in the same meaning as ^R 1 to R ⁶ of preferred embodiment is also the same.
In general formula (I-3), the substituents represented by R ^{8 to} R ¹³ are respectively synonymous with the substituents represented by R ^{1 to} R ⁶ of the compound represented by general formula (I). The preferable aspect is also the same.
When the substituents represented by R ^{8 to} R ¹³ of the compound represented by the general formula (I-3) are further substitutable groups, they may be substituted with any of the above-described substituents. When substituted with two or more substituents, the substituents may be the same or different.
^{R 7} in formula (I-3) has the same meaning as ^{R 7} in formula (I), preferable embodiments thereof are also the same.
R ¹⁴ in the general formula (I-3) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and a preferable range of R ^{14 is} the same as the preferable range of R ⁷ described above. When R ¹⁴ is a further substitutable group, it may be substituted with any of the substituents R described above, and when it is substituted with two or more substituents, those substituents are They may be the same or different.

  In General Formula (I-3), Ma represents a metal or a metal compound, and a metal atom or a metal compound in the above “complex in which the compound represented by General Formula (I) is coordinated to a metal atom or a metal compound” It is synonymous and the preferable range is also the same.

In general formula (I-3), R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹² and R ¹³ are each independently bonded to each other to form a 5-, 6-, or 7-member. A membered saturated ring or an unsaturated ring may be formed. The saturated ring or unsaturated ring formed is synonymous with the saturated or unsaturated ring formed by R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ^6. The preferred examples are also the same.
Further, in general formula (I-3), R ¹ and R ⁸ or R ¹³ preferably do not form a ring, and R ⁶ and R ⁸ or R ¹³ do not form a ring. Is preferred.

In the general formula (I-4), R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, Represents an aryl group or a heterocyclic group. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NR ^a (R ^a represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom. Or a sulfur atom. Y ¹ and Y ² each independently represent NR ^b (R ^b represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), oxygen. Represents an atom, sulfur atom, or carbon atom.
X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed.

Formula ^{(I-4) R 2 ~R} 5 in, and ^{R 7,} the general formula (I) ^R 2 ~R ⁵ in, and have the same meaning as ^{R 7,} preferred embodiments are also the same.
Ma in the general formula (I-4) represents a metal or a metal compound, and has the same meaning as the metal atom or the metal compound in the complex in which the compound represented by the general formula (I) is coordinated to the metal atom or the metal compound. The preferred range is also the same.

In General Formula (I-4), R ⁸ and R ⁹ are each independently an alkyl group (preferably a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms). For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl Group), an alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (preferably a carbon number). An aryl group having 6 to 36, more preferably 6 to 18, for example, a phenyl group or a naphthyl group, or a heterocyclic group (preferably having 1 to 24 carbon atoms, more preferably 1 to 1 carbon atoms). 2 heterocyclic groups such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, Triazol-1-yl group), an alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms such as methoxy group, ethoxy group, propyloxy group, butoxy group, hexyloxy group, 2 -Ethylhexyloxy group, dodecyloxy group, cyclohexyloxy group), aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 1 to 18, for example, phenoxy group, naphthyloxy group), alkylamino A group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms such as Ruamino group, ethylamino group, propylamino group, butylamino group, hexylamino group, 2-ethylhexylamino group, isopropylamino group, t-butylamino group, t-octylamino group, cyclohexylamino group, N, N-diethylamino Group, N, N-dipropylamino group, N, N-dibutylamino group, N-methyl-N-ethylamino group), arylamino group (preferably C6-C36, more preferably 6-18 aryl) Amino group, for example, phenylamino group, naphthylamino group, N, N-diphenylamino group, N-ethyl-N-phenylamino group), or heterocyclic amino group (preferably having 1 to 24 carbon atoms, more preferably 1-12 heterocyclic amino groups such as 2-aminopyrrole group, 3-aminopyrazole group, 2-aminopyridine Down group, a 3-aminopyridine group).

In general formula (I-4), the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, or heterocyclic amino group represented by R ⁸ and R ⁹ is In the case of further substitutable groups, they may be substituted with any of the above substituents R, and when substituted with two or more substituents, these substituents are the same. Or different.

In General Formula (I-4), X ³ and X ⁴ each independently represent NR ^a , an oxygen atom, or a sulfur atom. R ^a is a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or an isopropyl group. , Butyl group, isobutyl group, t-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), alkenyl group (preferably having 2 to 24 carbon atoms, More preferably, it is an alkenyl group having 2 to 12, for example, a vinyl group, an allyl group, a 3-buten-1-yl group), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms). A phenyl group, a naphthyl group), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, Enyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), acyl group ( Preferably it is a C1-C24, more preferably C2-C18 acyl group, for example, an acetyl group, a pivaloyl group, a 2-ethylhexyl group, a benzoyl group, a cyclohexanoyl group), an alkylsulfonyl group (preferably a carbon number of 1 To 24, more preferably an alkylsulfonyl group having 1 to 18, for example, methylsulfonyl group, ethylsulfonyl group, isopropylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably having 6 to 24 carbon atoms, more preferably 6). To 18 arylsulfonyl groups such as phenylsulfonyl group, It represents a Chirusuruhoniru group). Further, when R ^a can be substituted, it may be further substituted with a substituent, and when it is substituted with a plurality of substituents, these substituents may be the same or different.
X ³ and X ⁴ are preferably each independently an oxygen atom or a sulfur atom, and particularly preferably both X ³ and X ⁴ are oxygen atoms.

In General Formula (I-4), Y ¹ and Y ² each independently represent NR ^b , a sulfur atom, or a carbon atom, and R ^b has the same meaning as R ^a in X ³ .
Y ¹ and Y ² are preferably each independently NR ^b (R ^b is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and Y ¹ and Y ² are particularly preferably both NH.

In general formula (I-4), R ⁸ and Y ¹ are bonded to each other, and together with R ⁸ , Y ¹ , and carbon atom, a 5-membered ring (eg, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole) , Furan, thiophene, indole, benzofuran, benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline) Or a 7-membered ring (eg, cycloheptane, hexamethyleneimine).

In General Formula (I-4), R ⁹ and Y ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with R ⁹ , Y ² , and the carbon atom. Examples of the 5-membered, 6-membered, and 7-membered rings formed include rings in which one bond in the ring formed by R ⁸ , Y ^1, and a carbon atom is changed to a double bond.
In the general formula (I-4), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ⁸ and Y ¹ and R ⁹ and Y ² are further substitutable rings May be substituted with the group described in any of the above substituents R, and when it is substituted with two or more substituents, these substituents may be the same or different. Good.
In General Formula (I-4), X ⁵ represents a group capable of binding to Ma, and examples thereof include the same groups as X ² in General Formula (I-1). a represents 0, 1, or 2.

Preferred embodiments of the compound represented by formula (I-4) are shown below. That is, R ^{2 to} R ⁵ , R ⁷ and Ma are each a preferred embodiment of a complex containing a compound represented by the general formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are Each independently NR ^a (R ^a is a hydrogen atom, alkyl group, heterocyclic group) or an oxygen atom; Y ¹ and Y ² are each independently NR ^b (R ^b is a hydrogen atom or alkyl group), A nitrogen atom or a carbon atom, X ⁵ is an oxygen atom or a group bonded via a nitrogen atom, and R ⁸ and R ⁹ are each independently an alkyl group, an aryl group, a heterocyclic group, or an alkoxy group. Or an alkylamino group, or R ⁸ and Y ¹ are bonded to each other to form a 5- or 6-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5- or 6-membered ring. , A is an embodiment represented by 0 or 1.

The more preferable aspect of a compound represented by general formula (I-4) is shown below. That is, R ^{2 to} R ⁵ , R ⁷ and Ma are each a preferred embodiment of a complex containing a compound represented by the general formula (I) and a metal atom or a metal compound, and X ³ and X ⁴ are oxygen atoms. Y ¹ is NH, Y ² is a nitrogen atom, X ⁵ is an oxygen atom or a group bonded through a nitrogen atom, and R ⁸ and R ⁹ are each independently an alkyl group, Represents an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R ⁸ and Y ¹ are bonded to each other to form a 5-membered or 6-membered ring, and R ⁹ and Y ² are bonded to each other. A 5- or 6-membered ring is formed, and a is an embodiment represented by 0 or 1.

  In the general formula (I-2) to the general formula (I-4), the structure represented by the general formula (I) is a preferable embodiment of a dye which is a metal complex compound coordinated to a metal atom or a metal compound. Among the complex compounds represented, the compound represented by the general formula (I-4) is a particularly preferable embodiment.

Specific examples of the specific dye (A-1) represented by the general formula (I) used in the present invention are shown below. However, the present invention is not limited to these.
As will be apparent from the following specific examples, the specific dye (A-1) according to the present invention includes not only the dipyrromethene metal complex compound (monomer) represented by the general formula (I) but also the structure thereof. And a multimer containing as a partial structure.
In the following exemplary compounds 43 to 45, a / b and a / b / c represent mass ratios of the respective constituent components.

Among the exemplary compounds of these dipyrromethene metal complex compounds, exemplary compounds (46) to (50) are also exemplary compounds of general formula (I-2), and exemplary compound (51) is a compound of general formula (I-3). Exemplified compounds (1) to (45) are also exemplified compounds of the general formula (I-4).

  In addition to the above exemplary compounds, exemplary compounds (Ia-3) to (Ia-83), (Ia-1) to (IIa-20), (I-1) to (Ia) described in JP-A-2008-292970 (I-36) (II-1) to (II-11) and (III-1) to (III-103), Exemplified compounds (I-1) to (I-35) described in Japanese Patent No. 3324279 Exemplified compounds (I-1) to (I-13) described in Japanese Patent No. 3279035, Exemplified compounds (2-1) to (2-32) and (3-1) described in JP-A-11-256057 To (3-32), (4-1) to (4-26), and (5-1) to (5-26), exemplified compounds described in JP-A-2005-77953 (I-1) to ( I-6), and (VII-1) to (VII-8), described in JP-A-11-352686. Compounds (1-1) to (1-45), Exemplified compounds (1-1) to (1-50) described in JP-A No. 2000-19729, and Exemplified compounds described in JP-A No. 11-352585 ( 1-1) to (1-45) are also examples of dyes (dipyrromethene metal complex compounds) which are metal complex compounds in which the structure represented by the general formula (I) is coordinated to a metal atom or a metal compound.

  The content of the dye in the colored curable composition of the present invention is preferably 0.5 to 40% by mass, and preferably 1 to 30% by mass, based on the total solid content of the composition. More preferred. When the content of the dye is within the above range, various color designs are possible, and since the dye can be uniformly present in the colored curable composition without agglomerating, the high brightness of the dye itself. The characteristic that it is can be exhibited more.

-Specific alkali-soluble resin-
The colored curable composition of the present invention contains at least one specific alkali-soluble resin as a polymer dispersant.
The specific alkali-soluble resin includes a structural unit (b1) having a carboxyl group in a side chain, a compound represented by the following general formula (i) and a general formula (ii) in at least a part of the structural unit (b1). And a structural unit (b2) to which at least one compound selected from the represented compounds is added.

-Structural unit (b1)-
The structural unit (b1) having a carboxyl group in the side chain is a structural unit having a structural unit having a carboxyl group (including a carboxylic acid anhydride residue) in the side chain, and is included in the specific alkali-soluble resin.
As the structural unit (b1), for example, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and derived from unsaturated carboxylic acids such as dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid The structural unit to be mentioned can be mentioned as a preferable thing.
Moreover, as a structural unit which has a carboxylic anhydride residue, the structural unit derived from maleic anhydride, itaconic anhydride, etc. can be mentioned as a preferable thing, for example. These structural units are made into a copolymer and then hydrolyzed, so that the obtained copolymer becomes a copolymer having carboxyl in the side chain.

  Among these, structural units derived from acrylic acid and methacrylic acid are more preferable. The structural unit which has these carboxyl groups can be used individually by 1 type or in combination of 2 or more types.

-Structural unit (b2)-
The structural unit (b1) has a side chain added with at least one compound selected from a compound represented by the following general formula (i) and a compound represented by the general formula (ii). Unit (b2) is constructed.

  In general formula (i) and general formula (ii), Z represents a hydrogen atom or a methyl group.

The specific alkali-soluble resin in the present invention is selected from a compound represented by the general formula (i) and a compound represented by the general formula (ii) in a part of the structural unit (b1) having a carboxyl group in the side chain. It is synthesized by adding at least one compound. The carboxyl group of the structural unit (b1) reacts with the epoxy ring of at least one compound selected from the compound represented by the general formula (i) and the compound represented by the general formula (ii), and the general formula At least one compound selected from the compound represented by (i) and the compound represented by formula (ii) is added.
Since the colored photosensitive composition of the present invention can increase the curing sensitivity by including the structural unit (b2) in the specific alkali-soluble resin, the pattern forming property is improved, and the resulting color filter has a stripping solution resistance. Will improve. In particular, when a specific alkali-soluble resin containing a structural unit obtained by adding the compound represented by the general formula (i) to the structural unit (b1) is used as the structural unit (b2), the relative dielectric constant can be reduced.

  Z in general formula (i) and general formula (ii) is preferably a methyl group. Moreover, it is especially preferable to add the compound represented by general formula (i) among the compound represented by general formula (i) and the compound represented by general formula (ii).

In addition, the structural unit (b1) in the specific alkali-soluble resin is obtained by adding at least one compound selected from the compound represented by the general formula (i) and the compound represented by the general formula (ii) to the structural unit ( b2), but at least one compound selected from the compound represented by the general formula (i) and the compound represented by the general formula (ii) is not added, that is, in an unreacted state (carboxyl It may be contained in the specific alkali-soluble resin (with a group), and the specific alkali-soluble resin preferably contains the structural unit (b1) itself.
By including the structural unit (b1) itself, the specific alkali-soluble resin can exhibit alkali-solubility, and a latent image obtained by exposure is formed as a colored pattern by development in contact with a developer such as an alkaline aqueous solution. Can do.

  The content of the structural unit (b2) in the specific alkali-soluble resin is preferably 0.1% to 70%, more preferably 10% to 40%, and more preferably 15% to 40% on a mass basis. .

(Other structural units contained in specific alkali-soluble resins)
The specific alkali-soluble resin contains other structural units other than the structural unit (b1) and the structural unit (b2) (hereinafter, appropriately referred to as “other structural units”) as long as the effects of the present invention are not hindered. It is preferable to do.

-Structural unit (b3)-
The copolymerizable monomer used to form other structural units is preferably a polymerizable monomer having an alicyclic alkyl group, and is a polymerizable monomer having a polycyclic alicyclic alkyl group. More preferably. The structural unit derived from the polymerizable monomer having an alicyclic alkyl group is hereinafter referred to as “structural unit (b3)”.
By containing the structural unit (b3), the specific alkali-soluble resin of the present invention can improve the pattern formability, reduce the relative dielectric constant of the obtained color filter, and improve the resistance to the peeling solution. be able to.

  Furthermore, although the dielectric constant of the colored layer using the colored photosensitive composition of the present invention is small, this is selected from the compound represented by the general formula (i) and the compound represented by the general formula (ii). It is considered that the structural unit (b2) has a group derived from at least one kind of compound in the side chain, and the specific alkali-soluble resin has the structural unit (b3). It is estimated that b3) was effectively exhibited by the structural unit having a polycyclic alicyclic alkyl group, particularly a tricyclodecanyl group or a dicyclopentadienyl group in the side chain.

  Among polymerizable monomers having an alicyclic alkyl group, examples of the polymerizable monomer having a monocyclic alicyclic alkyl group include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, (meth) Cyclopentyl acrylate, 2-methylcyclopentyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (Meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate and the like can be mentioned.

  Examples of the polymerizable monomer having a polycyclic alicyclic alkyl group include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentayl. Pentenyloxyethyl (meth) acrylate, cyclopentyl (meth) acrylate, dicyclohexanyl (meth) acrylate, dicyclohexenyl (meth) acrylate, dicyclohexanyloxyethyl (meth) acrylate, dicyclohexenyloxyethyl (meth) Acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pinenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclo 5.2.1.02,6] decan-8-yl (meth) acrylate, tricyclo [5.2.1.0 2,6] decane-8-yl oxy ethyl (meth) acrylate.

  Of these polymerizable monomers having an alicyclic alkyl group, a polymerizable monomer having a polycyclic alicyclic alkyl group is more preferable, and a tricyclodecanyl group or dicyclopentadienyl is more preferable. A polymerizable monomer having a group is preferred.

-Structural unit (b4)-
Furthermore, the specific alkali-soluble resin in the present invention is a structural unit derived from a polymerizable monomer having a structure different from that of the structural units (b1) to (b3) such as alkyl (meth) acrylate, aryl (meth) acrylate, vinyl compound, etc. It is preferable to appropriately include “structural unit (b4)”.
By containing the structural unit (b4), the specific alkali-soluble resin of the present invention improves the organic solvent solubility when preparing a colored photosensitive composition, and facilitates pattern formation of the resulting color filter. In addition, the stripping solution resistance can be improved.

The structural unit (b4) is not particularly limited as long as the solubility of the specific alkali-soluble resin in the organic solvent is improved.
Examples of the polymerizable monomer used to form the structural unit (b4) include alkyl (meth) acrylates in which hydrogen atoms of the alkyl group and aryl group may be substituted with substituents, and aryl (meth) Acrylate, CH ₂ ═C (R ¹¹ ) (COOR ¹³ ) [wherein R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ¹³ represents an alkyl group having 1 to 8 carbon atoms or An aralkyl group having 6 to 12 carbon atoms is represented. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) ) Acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is an alkyl group having 1 to 8 carbon atoms) ), Hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

As these polymerizable monomers, polymerizable monomers having a polyalkylene oxide chain can also be used. The polyalkylene oxide chain may be a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof.
1-20 are preferable and, as for the number of repeating units of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable. Acrylic copolymers having a polyalkylene oxide chain in these side chains are, for example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Poly (ethylene glycol-propylene glycol) mono (meth) acrylate and the like, and compounds in which these terminal OH groups are alkyl-blocked, such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly (ethylene glycol) -Propylene glycol) mono (meth) acrylate and the like are also preferred.

  Examples of vinyl compounds include aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene, nitrile vinyl compounds such as (meth) acrylonitrile and α-chloroacrylonitrile, N-cyclohexylmaleimide, and N-benzylmaleimide. And maleimide compounds such as N-phenylmaleimide.

Among the above polymerizable monomers that form the structural unit (b4), methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, styrene, glycerol monomethacrylate, allyl methacrylate, glycidyl methacrylate, Methacrylic acid.
The polymerizable monomer forming the structural unit (b4) contained in the specific alkali-soluble resin may be one type or two or more types.

  As a preferable combination of the structural units (b1) to (b4) in the specific alkali-soluble resin, the structural unit (b1) is methacrylic acid or acrylic acid, and the structural unit (b2) is 3,4-epoxycyclohexyl methacrylate. And the structural unit (b3) is preferably dicyclopentanyl methacrylate and the structural unit (b4) is preferably benzyl methacrylate.

  As a preferable composition ratio of the structural unit (b1): the structural unit (b2): the structural unit (b3): the structural unit (b4) in the specific alkali-soluble resin, 0 to 40: It is preferably 10 to 40: 0 to 30:30 to 70, and more preferably 25 to 40:15 to 40: 0 to 30: 0 to 60. The effect of this invention can be show | played by setting it as this range.

  The weight average molecular weight of the specific alkali-soluble resin in the present invention is preferably 5000 to 50000, more preferably 5000 to 40000, and further preferably 8000 to 30000. In addition, it is preferable that the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).

  The specific alkali-soluble resin of the present invention is obtained by copolymerizing the polymerizable monomers forming the structural units (b1) and (b3) to (b4), and adding the copolymer obtained by the copolymerization to the general formula (i ) And at least one compound selected from the compounds represented by the general formula (ii) are reacted and added to at least a part of the structural unit (b1). As a synthesis method, for example, JP-A-2006-124664 can be referred to.

  Although the preferable specific example of specific alkali-soluble resin is shown below, this invention is not restrict | limited to these examples. In the following specific examples, m, n, p, q, and r represent mass%.

m: n: p: q = 30: 10: 35: 25 Mw: 9000

m: n: p: q = 30: 10: 25: 35 Mw: 9000

m: n: p: q: r = 25: 10: 25: 30: 10 Mw: 10000

A structural unit in which methacrylic acid / benzyl methacrylate / 3,4-epoxycyclohexyl methacrylate is added to methacrylic acid (composition ratio = 25/60/15, Mw: 9000)
A structural unit in which methacrylic acid / allyl methacrylate / 3,4-epoxycyclohexyl methacrylate is added to methacrylic acid (composition ratio = 30/40/30, Mw: 8000)
A structural unit in which acrylic acid / benzyl methacrylate / 3,4-epoxycyclohexyl methacrylate is added to acrylic acid (composition ratio = 25/60/15, Mw: 9000)
A structural unit in which acrylic acid / allyl methacrylate / 3,4-epoxycyclohexyl methacrylate is added to acrylic acid (composition ratio = 30/40/30, Mw: 8000)

  The content of the specific alkali-soluble resin with respect to the total solid content of the colored photosensitive composition is preferably 1 to 70% by mass, more preferably 5 to 60% by mass in terms of mass. By setting it as this range, the effect of this invention can be show | played, especially alkali solubility can be maintained and a brightness fall can be suppressed.

-Polymerizable compound-
The colored curable composition of the present invention contains at least one polymerizable compound. The polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected and used from components constituting a known composition. Japanese Patent Application Laid-Open No. 2006-23696 And the components described in paragraph numbers [0027] to [0053] of JP-A No. 2006-64921.

In addition, a urethane-added polymerizable compound produced by using an addition reaction between an isocyanate and a hydroxyl group is also suitable. JP-A-51-37193, JP-B-2-32293, JP-B-2-16765 And the ethylene oxide skeletons described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Urethane compounds having them are also suitable.
Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with acrylic acid. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate. , Pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc., as well as commercial products, NK ester A-TMMT, NK ester A-TMM-3, NK oligo UA -32P, NK Oligo UA-7200 (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix Preferable examples include M-402, TO-1382, TO-2349 (manufactured by Toagosei Co., Ltd.) and V # 802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  Furthermore, examples of the polymerizable compound include components described in paragraph numbers [0031] to [0061] of JP-A-2009-265630 from the viewpoint of low-temperature curability. Especially, (1)-(20) and (M-1)-(M-8) shown below can be mentioned as a preferable example.

  The said polymeric compound can be used individually or in combination of 2 or more types.

  The content of the polymerizable compound (total content in the case of two or more types) is preferably 10% by mass to 80% by mass, and 15% by mass to 75% by mass with respect to the total solid content in the colored curable composition. Is more preferable, and 20% by mass to 60% by mass is particularly preferable.

-Photopolymerization initiator-
The colored curable composition of the present invention preferably contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
The photopolymerization initiator is a compound that is exposed to exposure light and starts and accelerates polymerization of the polymerizable compound. A compound that responds to actinic rays having a wavelength of 300 nm or longer and initiates and accelerates polymerization of the polymerizable compound is preferable. In addition, a photopolymerization initiator that does not directly respond to actinic rays having a wavelength of 300 nm or longer can also be preferably used in combination with a sensitizer.

Specifically, for example, oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexa Examples thereof include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxide), benzophenone compounds, acetophenone compounds, and derivatives thereof.
Among these, an oxime ester compound and a hexaarylbiimidazole compound are preferable in terms of sensitivity.

  Examples of the oxime ester compound include JP 2000-80068, JP 2001-233842, JP 2004-534797, WO 2005/080337, WO 2006/018933, JP The compounds described in JP 2007-210991 A, JP 2007-231000 A, JP 2007-2699779 A, JP 2009-191061 A, and International Publication No. 2009/131189 can be used.

  Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) 9H- carbazol-3-yl] ethanone, and the like. However, it is not limited to these.

  In the present invention, a compound represented by the following general formula (A) is also suitable as an oxime ester compound that is a photopolymerization initiator from the viewpoint of sensitivity, stability over time, and coloring during post-heating.

In the general formula (A), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ is —R, —OR, —COR, —SR, —CONRR. 'Or -CN, R ² and R ³ are each independently. -R, -OR, -COR, -SR, or -NRR 'is represented. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. One or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be substituted with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. To form a ring.

In general formula (A), when X ¹ , X ² , and X ³ represent a halogen atom, examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and X ¹ , X ² , and X ³ are alkyl. Examples of the alkyl group in the case of representing a group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2- Ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxypropyl, Monofluoromethyl, difluoromethyl, Fluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2'-yl) ethenyl and the like.
Among these, it is preferable that all of X ¹ , X ² and X ³ represent a hydrogen atom, or X ¹ represents an alkyl group, and X ² and X ³ both represent a hydrogen atom.

In the general formula (A), examples of the alkyl group represented by R and R ′ include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, Hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxy Examples include ethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like.
Examples of the aryl group represented by R and R ′ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like.
Examples of the aralkyl group represented by R and R ′ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like.
Examples of the heterocyclic group represented by R and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl and the like.
Examples of the ring formed by bonding R and R ′ to each other include a piperidine ring and a morpholine ring.

R ² and R ^{3 including} R and R ′ are each independently a methyl group, a hexyl group, a cyclohexyl group, —S—Ph, —S—Ph—Cl, and —S—Ph—. Br is a particularly preferred embodiment.

Among the photopolymerization initiators, in general formula (A), X ¹ , X ² , and X ³ are all hydrogen atoms; R ¹ is an alkyl group, particularly a methyl group; R ² is alkyl Particularly preferred as photoinitiators are those which are groups, in particular methyl groups; those in which R ³ is an alkyl group, in particular ethyl group.

  Therefore, preferred specific examples of the photopolymerization initiator represented by the general formula (A) include compounds A to F exemplified below. However, the present invention is not limited by the following compounds.

  The photopolymerization initiator represented by the general formula (A) can be synthesized, for example, by the method described in JP-A-2005-220097.

  The compound represented by the general formula (A) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

  In the present invention, a compound represented by the following general formula (B) is also suitable as an oxime ester compound that is a photopolymerization initiator from the viewpoint of sensitivity, stability over time, and coloring during post-heating.

In the general formula (B), R ²² represents a monovalent substituent. A ²² represents a divalent linking group, and Ar represents an aryl group. n is an integer of 0-5. X ²² represents a monovalent substituent, and when n is an integer of 2 to 4, a plurality of X ²² may be the same or different.

The monovalent substituent represented by R ²² is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R ²² include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkylsulfonyl group that may have a substituent, Examples thereof include an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, a heterocyclic group which may have a substituent, and the like.

  The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, or a trifluoromethyl group. Etc.

  The aryl group that may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group and an ethylsulfonyl group.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, a thienyl group, a furyl group, a pyranyl group, etc. are mentioned.

R ²² is more preferably an unsubstituted or substituted acyl group from the viewpoint of high sensitivity, and specifically, an unsubstituted or substituted acetyl group, propionyl group, benzoyl group, toluyl group. Groups are preferred.
As said substituent, the group represented by the following structural formula is mentioned, for example, Among these, any of (d-1) (d-4) and (d-5) is preferable.

As the divalent linking group represented by A ²² is alkylene having 1 to 12 carbon atoms which may have a substituent, which may cyclohexylene have a substituent or may have a substituent Alkynylene is mentioned.
Examples of the substituent that can be introduced into these groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Examples include aryloxy groups such as a tolyloxy group, alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group.

Among these, the A ²² is an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Substituted alkylene group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl) Group, a styryl group) is preferable.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.
Specifically, Ar is phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m. -, P-cumenyl group, mesityl group, etc. are mentioned. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen atoms such as a fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy such as methoxy group, ethoxy group and tert-butoxy group. Groups, phenoxy groups, aryloxy groups such as p-tolyloxy groups, methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acetoxy groups, propionyloxy groups, acyloxy groups such as benzoyloxy groups, acetyl groups, Benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methacrylyl group and other acyl groups, methylamino group, cyclohexylamino group and other alkylamino groups, dimethylamino group, diethylamino group, morpholino group, piperidino group and other dialkylamino groups, Fe Arylamino group, a methyl group, an ethyl group, tert- butyl group, an alkyl group such as a dodecyl group, a hydroxy group, a carboxy group, and the like.

  In the general formula (B), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.

The monovalent substituent represented by X ^22, optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkenyl group, a substituted group An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, and a substituent A good arylthiooxy group, a halogen atom and the like can be mentioned.

  The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl. Group, 2-ethylhexyl group, phenacyl group and the like.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable. For example, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a terphenyl group, a quarterphenyl group, o-, m-, and p-tolyl groups, xylyl groups, and the like.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and a benzyloxy group. .

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, Examples include 2-methylphenyloxy group and 2-methoxyphenyloxy group.

  The alkylthiooxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms. For example, a methylthiooxy group, an ethylthiooxy group, a propylthiooxy group, an isopropylthiooxy group, a butylthiooxy group Group, isobutylthiooxy group, sec-butylthiooxy group, tert-butylthiooxy group, pentylthiooxy group, isopentylthiooxy group, hexylthiooxy group, heptylthiooxy group, octylthiooxy group, 2-ethylhexyl Examples include a thiooxy group, a decylthiooxy group, a dodecylthiooxy group, an octadecylthiooxy group, and a benzylthiooxy group.

  The arylthiooxy group which may have a substituent is preferably an arylthiooxy group having 6 to 30 carbon atoms, such as a phenylthiooxy group, a 1-naphthylthiooxy group, a 2-naphthylthiooxy group, 2 -Chlorophenylthiooxy group, 2-methylphenylthiooxy group, 2-methoxyphenylthiooxy group, 2-butoxyphenylthiooxy group, 3-chlorophenylthiooxy group, 3-trifluoromethylphenylthiooxy group, 3-cyano Phenylthiooxy group, 3-nitrophenylthiooxy group, 4-fluorophenylthiooxy group, 4-cyanophenylthiooxy group, 4-methoxyphenylthiooxy group, 4-dimethylaminophenylthiooxy group, 4-methylsulfanyl Phenylthiooxy group, 4-phenylsulfanylphenyl Thiooxyacids group, and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the halogenated alkyl group which may have a substituent include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group, and a tribromomethyl group. Etc.

  Examples of the amide group which may have a substituent on N include N, N-dimethylamide group and N, N-diethylamide group.

Among these, X ²² has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio which may have a substituent Oxy group, arylthiooxy group which may have a substituent, halogenated alkyl group which may have a substituent, amino group which may have a substituent, or a substituent on N A good amide group is preferable, and an alkyl group which may have a substituent is more preferable.

Moreover, although n in general formula (B) represents the integer of 0-5, the integer of 0-3 is preferable from a viewpoint of the ease of a synthesis | combination, and the integer of 0-2 is more preferable.
In Formula (B), if X ²² there are a plurality, the plurality of X ²² may be the same or may be different.

  Specific examples of the oxime photopolymerization initiator represented by the general formula (B) are shown below.

  The compound represented by the general formula (B) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, and Japanese Examined Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970), and particularly, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  Examples of hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Various compounds described in the specification, specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o- Bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5'-tetraphenyl Imidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  A photoinitiator can be used 1 type or in combination of 2 or more types. When using 2 or more types, multiple types of compounds represented by general formula (B) may be used, and multiple types of compounds represented by general formula (II) may be used. Moreover, you may use at least 1 sort (s) from the compound represented by general formula (II) and (III), respectively. In addition, at least one of the compounds represented by the general formulas (II) and (III) and an oxime compound other than the compounds represented by the general formulas (II) and (III) or photopolymerization other than the oxime compound are started. An agent may be used. Moreover, you may use a sensitizer together.

  The total content of the photopolymerization initiator is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 10% by mass with respect to the total solid content in the colored curable composition. More preferably, 1% by mass to 5% by mass is most preferable. Within this range, the sensitivity during exposure is high and the color characteristics are also good.

-Binder-
The colored curable composition of the present invention may contain a binder in addition to the resin that is a copolymer containing a repeating unit having an N-substituted maleimide group in order to improve the film-forming property.
As a binder, it is preferable to use an alkali-soluble thing from a viewpoint of pattern formation, and it is preferable to select from viewpoints, such as heat resistance, developability, and availability.
That is, other alkali-soluble binders may be used in combination with the specific alkali-soluble resin as long as the effects of the present invention are not impaired.

  The other alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  In addition to the above, other alkali-soluble binders include those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate) Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol and the like are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include chain butyl (meth) acrylate or phenoxyhydroxypropyl (meth) acrylate. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

  Further, other alkali-soluble binders may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. Polymers contained in are also useful. Examples of the polymer containing a polymerizable group described above include: NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (manufactured by COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd.), Biscote R-264. KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.) and the like. It is done. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various other alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and developability. From the viewpoint of control, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferred.

  Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, the above Photomer 6173, and KS resist-106. Cyclomer P series and the like are preferable.

The other alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ from the viewpoint of developability, liquid viscosity, etc., and 2000 to 1 × 10. ⁵ is more preferable, and 5000 to 5 × 10 ⁴ is particularly preferable. It can be used alone or in combination of two or more.

-Other ingredients-
As long as the colored curable composition of the present invention does not impair the effects of the present invention, if necessary, further known additives such as polyfunctional thiol compounds, chain transfer agents, polymerization inhibitors, organic solvents, An additive such as a surfactant, an adhesion improver, a crosslinking agent, and a development accelerator may be contained.

(Polyfunctional thiol compound)
The colored curable composition of the present invention may contain a polyfunctional thiol compound.
The colored curable composition of the present invention includes a polyfunctional thiol compound, so that the sensitivity is increased, ion elution caused by a coloring material such as a dye is suppressed, and the colored curing of the present invention is used for producing a color filter of a liquid crystal display device. When the composition is used, image quality deterioration such as crosstalk can be prevented, and a clear and high-quality display can be achieved.

  In the present invention, the “polyfunctional thiol compound” means a compound having two or more thiol groups in the molecule. As the polyfunctional thiol compound, a low molecular compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1500 is preferable, and 150 to 1000 is more preferable. The polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, and more preferably 2 to 6 thiol groups. In addition, these compounds are preferably used as a system that is used auxiliary when the radical polymerizable monomer is polymerized. Specifically, the addition amount of the polyfunctional thiol compound is 1 to 20% by mass relative to the total solid content of the composition, or less than the addition amount of the radical polymerizable monomer contained at the same time. It is preferable to make it an addition amount.

  Specific examples of suitable polyfunctional thiol compounds that can be used in the present invention include, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptobutyrate), butanediol bis (3-mercapto) Butyrate), 1,4-bis (3-mercaptobutyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, etc. That.

  The content of the polyfunctional thiol compound is preferably 0.01 to 20% by mass and more preferably 0.1 to 10% by mass with respect to the total solid content in the colored curable composition. When the content of the polyfunctional thiol compound is in this range, the sensitivity of the colored curable composition is good, the storage stability is good, the pixel adhesion in the obtained color filter is good, and there is no pattern defect. When used in a liquid crystal display device, a colored curable composition having good electrical characteristics can be provided.

(Sensitizer)
A sensitizer can also be added to the colored curable composition of the present invention. Typical sensitizers that can be used in the present invention include those disclosed in Crivello [JV Crivello, Adv. In Polymer Sci, 62, 1 (1984)]. Perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavin, N-vinylcarbazole, 9,10-dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like. The sensitizer is preferably added in a proportion of 50 to 200% by mass with respect to the photopolymerization initiator.

(Chain transfer agent)
A chain transfer agent can also be added to the colored curable composition of the present invention. Examples of the chain transfer agent that can be used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, Examples include mercapto compounds having a heterocyclic ring such as 2-mercaptobenzimidazole and N-phenylmercaptobenzimidazole.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
The addition amount of the chain transfer agent is preferably in the range of 0.01 to 15% by mass with respect to the total solid content of the colored curable composition of the present invention, from the viewpoint of reducing sensitivity variation. 1-10 mass% is more preferable, and 0.5-5 mass% is especially preferable.

(Polymerization inhibitor)
The colored curable composition of the present invention may contain a polymerization inhibitor.
The polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to polymerization initiation species such as radicals generated in the colored curable composition by light or heat. , Electron donation) and the like, deactivate the polymerization initiating species, and suppress the unintentional initiation of the polymerization. For example, polymerization inhibitors described in paragraphs 0154 to 0173 of JP2007-334322A can be used.
Among these, p-methoxyphenol is preferably exemplified as the polymerization inhibitor.
The content of the polymerization inhibitor in the colored curable composition of the present invention is preferably 0.0001 to 5% by mass, more preferably 0.001 to 5% by mass with respect to the total mass of the polymerizable compound. 001 to 1% by mass is particularly preferable.

(Organic solvent)
The colored curable composition of the present invention can contain an organic solvent.
The organic solvent is not basically limited as long as it can satisfy the solubility of each of the coexisting components and the coating property when it is a colored curable composition. It is preferable to select in consideration of applicability and safety.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. Oxyacetic acid alkyl esters (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate). )), 3-oxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate Propylpyruvate, a DOO methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl methyl ether. Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferred examples of aromatic hydrocarbons include toluene and xylene.

  When these organic solvents contain the solubility of each component described above and an alkali-soluble binder, it is preferable to mix two or more of them from the viewpoints of the solubility and the improvement of the coated surface. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, It is a mixed solution composed of two or more selected from cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The content of the organic solvent in the colored curable composition of the present invention is preferably such that the total solid concentration in the colored curable composition is 10% by mass to 80% by mass, and 15% by mass to 60%. It is more preferable that the amount becomes mass%.

(Surfactant)
The colored curable composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph 0058 of JP-A-2009-098616, and among these, fluorosurfactants are preferable.
Other surfactants that can be used in the present invention include, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554. F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (made by DIC Corporation), Florard FC-135, FC -170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131 S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Footgent 250 (manufactured by Neos Co., Ltd.), etc. Is mentioned.
Further, as the surfactant, the structural unit A and the structural unit B represented by the following formula (W) are included, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent is 1, A copolymer having a molecular weight of 000 or more and 10,000 or less can be given as a preferred example.

(In the formula (W), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 4 or less, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p represents a numerical value of 10% to 80% by mass. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.

The L is preferably a branched alkylene group represented by the following formula (W-2). R ⁵ in Formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. Two or three alkyl groups are more preferred.
The sum (p + q) of p and q in the formula (W-2) is preferably p + q = 100, that is, 100% by mass.
The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

These surfactants can be used alone or in combination of two or more.
The addition amount of the surfactant in the colored curable composition of the present invention is preferably 0.01 to 2.0% by mass, particularly 0.02 to 1.0% by mass in the total solid content of the colored curable composition. preferable. Within this range, the coatability and the uniformity of the cured film are good.

(Adhesion improver)
The colored curable composition of the present invention may contain an adhesion improving agent.
The adhesion improver improves the adhesion between the inorganic material serving as the support, for example, a silicon compound such as glass, silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the cured film of the colored curable composition layer. A compound. Specific examples include silane coupling agents. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and among them, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
The content of the adhesion improving agent in the colored curable composition of the present invention is preferably 0.1 to 20% by mass and more preferably 0.2 to 5% by mass with respect to the total solid content of the colored curable composition. .

(Crosslinking agent)
In the colored curable composition of the present invention, a crosslinking agent can be supplementarily used to further increase the hardness of the colored layer obtained by curing the colored curable composition.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, substituted with at least one selected substituent And phenolic compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.
For details of specific examples and the like of the crosslinking agent, the description in paragraphs [0134] to [0147] of JP-A No. 2004-295116 can be referred to.

(Development accelerator)
A development accelerator can also be added in order to promote the alkali solubility of the non-exposed region when the colored curable composition layer is exposed and to further improve the developability of the colored curable composition. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.

(Other additives)
If necessary, the colored curable composition of the present invention may further contain various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, antioxidants and the like. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
The colored curable composition of the present invention can contain the light stabilizer described in paragraph [0078] of JP-A No. 2004-295116 and the thermal polymerization inhibitor described in paragraph [0081] of the same publication. .

[Method for producing colored curable composition]
The colored curable composition of the present invention comprises the organic pigment, the dye containing a mother skeleton different from the organic pigment, adsorbed on the surface of the organic pigment, and the repeating unit having the N-substituted maleimide group. It is produced by mixing a copolymer containing, a solvent, and if necessary, an optional component through a process of dispersing the organic pigment in the solvent in the presence of at least the dye.
If the organic pigment is dispersed in the solvent before the dye is added, the dye is difficult to adsorb on the surface of the organic pigment. Therefore, before or simultaneously with dispersing the organic pigment in the solvent, the organic pigment and the dye are brought into contact with each other to obtain an organic pigment having the dye adsorbed on the surface.

  The colored curable composition of the present invention includes, for example, a pigment dispersion containing at least the organic pigment, the dye, a copolymer containing a repeating unit having the N-substituted maleimide group, and a solvent ( Hereinafter, it is also referred to as a dispersion composition.) After preparing the pigment dispersion, the above-described polymerizable compound, photopolymerization initiator, binder, and other components that may be included as necessary are mixed. Can be manufactured.

The dispersion composition is a process in which an organic pigment is dispersed in a solvent in the presence of at least a dye, and the organic pigment, the dye, a copolymer containing a repeating unit having an N-substituted maleimide group, and a solvent. And the organic pigment having the dye adsorbed on the surface is dispersed. The dispersion composition is manufactured through such a mixing and dispersing step, and various mixers and dispersers are used in this step.
The mixing and dispersing step is preferably configured by providing at least a kneading dispersion for kneading and dispersing the dye, the organic pigment, and a solvent, followed by a fine dispersion treatment for fine dispersion. It is more preferable that the fine dispersion treatment is configured by providing a two-stage dispersion treatment (coarse dispersion and precision dispersion). Depending on the material to be mixed and dispersed and the target performance, for example, it is possible to omit a part of the processing, such as omitting the kneading and dispersing and performing only the fine dispersion processing.

  The dispersion composition can be produced, for example, by the following method. First, the dye solution is mixed with the solvent to prepare a dye solution. Next, in the dye solution, the organic pigment, a polymer dispersant such as a copolymer or a pigment derivative containing a repeating unit having the N-substituted maleimide group, and other optional components as necessary. After adding, using a dispersing machine such as a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., fine dispersion treatment is performed with beads made of glass, zirconia, etc. with a particle diameter of 0.01 mm to 1 mm. By performing this, the dispersion composition can be obtained.

  In the method for producing the dispersion composition, before performing the fine dispersion treatment with the beads described above, two-roll, three-roll, ball mill, tron mill, disper, kneader, conider, homogenizer, blender, single screw or twin screw extrusion It is also possible to carry out a kneading and dispersing process by kneading and dispersing using a machine or the like while applying a strong shearing force. The details of kneading and dispersing are described in “Paint Flow and Pigment Dispersion” by TC Patton (1964, published by John Wiley and Sons), etc., and the method described here is also applied in the present invention. be able to.

  When dispersion is performed using a bead mill, the organic pigment before dispersion often forms aggregates. Therefore, the dispersion process is divided into, for example, a two-stage process in which the diameter of the beads used is changed (the coarse dispersion and the fine dispersion described above), and a large aggregate is crushed or deagglomerated by the first-stage dispersion. By obtaining the target degree of dispersion by eye dispersion, the efficiency of dispersion can be improved.

As described above, in the method for producing a colored curable composition of the present invention, the organic pigment, the dye, a copolymer containing a repeating unit having an N-substituted maleimide group, and a solvent are mixed. At the time, the organic pigment is dispersed in the presence of at least a dye. In this process, at least the organic pigment and the dye are kneaded together with a solvent, and the obtained kneaded material is further mixed with a solvent to disperse the organic pigment. First, by mixing the organic pigment and the dye together with the solvent, the concentration of the dye around the organic pigment increases, the adsorption of the dye to the organic pigment is promoted, and more dye is adsorbed on the surface of the organic pigment. As a result, the heat resistance of the dye is further improved.
The solvent used for kneading and the solvent mixed with the obtained kneaded product may be of the same type or different types, but when different types of solvents are used. It is preferable to use a compatible solvent.

  The dye for kneading with the organic pigment may be in a state dissolved in a solvent, but is preferably in a solid state if possible in terms of solubility and the like. This is because the dye concentration in contact with the organic pigment before or at the time of dispersion is preferably as high as possible. As described above, the higher the concentration of the dye around the organic pigment before or at the time of dispersion, the more the adsorption of the dye to the organic pigment is promoted, and as a result, the heat resistance of the dye is improved. The performance of improving the hue and luminance of the display image inherent to the dye can be sufficiently exhibited, and the formation of a colored and hardened film with high luminance can be realized. From such a viewpoint, the dye is preferably added in a solid state during the kneading dispersion or the coarse dispersion treatment in the production of the dispersion composition, and the dye in this case is represented by the general formula (I). It is more preferable that the compound represented by is a metal atom or a complex coordinated to a metal compound (dipyrromethene metal complex compound).

  The colored curable composition produced as described above can preferably be used after being filtered using a filter having a pore diameter of about 0.01 μm to 3.0 μm.

  According to the colored curable composition of the present invention, a change in chromaticity due to heating or chemicals hardly occurs, and a colored cured film having high luminance can be formed. Moreover, according to the colored curable composition of the present invention, a colored cured film having a low relative dielectric constant and a high resistance to a peeling solution can be formed. Therefore, the colored curable composition of the present invention can be suitably used for forming colored pixels such as a color filter used in a liquid crystal display device, and for producing printing ink, inkjet ink, paint, and the like.

<< Color filter and manufacturing method thereof >>
The color filter of the present invention includes a substrate and a colored pixel composed of a colored film formed on the substrate by the colored curable composition of the present invention. The colored region on the substrate is composed of colored layers such as red (R), green (G), and blue (B) that form each pixel of the color filter.

The color filter of the present invention is formed by a colored layer forming step of forming the colored layer (colored curable composition layer) by applying the colored curable composition on a support and the colored layer forming step. It can be produced by a method including an exposure step of pattern-like exposure to the colored layer and a development step of developing the exposed colored layer to form a pattern.
Moreover, in the manufacturing method of the color filter of this invention, the aspect which further provided the post-baking process (post-heating process) which heat-processes with respect to the colored pattern obtained at the image development process is preferable. When providing a colored pattern of a plurality of colors, the post-baking step may be performed after the colored pattern of the last color is provided.
Furthermore, it is also possible to provide a step (post-exposure step) of irradiating the colored pattern with ultraviolet rays between the development step and the post-bake step.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.

  First, a method of manufacturing a color filter for a liquid crystal display device of a conventionally used method will be described, and then a color for a color filter on array (COA) method of a liquid crystal display device that is effective in terms of improving luminance and yield. A method for manufacturing the filter will also be described.

[Color filter manufacturing method]
-Colored layer formation process-
In the method for producing a color filter of the present invention, first, the above-described colored curable composition of the present invention is applied onto a support by spin coating, slit coating, cast coating, roll coating, bar coating, ink jet, or the like. To form a colored layer, and then the colored layer is dried by heating (prebaking) or vacuum drying.

Examples of the support include soda glass, non-alkali glass, borosilicate glass, quartz glass, a silicon substrate, a resin substrate, and the like used in liquid crystal display devices. As a support used for a color filter for a COA type liquid crystal display device described later, for example, a driving substrate for a thin film transistor (TFT) type liquid crystal display device is used.
On these supports, if necessary, an undercoat layer, an interlayer insulating film, or the like may be provided in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the surface.

Examples of the pre-baking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
Moreover, the thickness (film thickness after drying) of the colored layer formed by the colored curable composition is appropriately selected according to the purpose. In the color filter for liquid crystal display devices, the thickness of the colored layer is preferably in the range of 0.2 μm to 5.0 μm, and more preferably in the range of 1.0 μm to 4.0 μm.
In the color filter for COA type liquid crystal display device described later, the thickness (film thickness after drying) of the colored layer is preferably in the range of 0.3 μm to 5.0 μm, and in the range of 0.5 μm to 3.5 μm. Further preferred.

-Exposure process-
Subsequently, in the method for producing a color filter of the present invention, pattern-like exposure is performed on the colored layer formed on the support. As light or radiation applicable to exposure, g-line, h-line, i-line and various laser beams are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of ^{5mJ / cm 2 ~500mJ / cm 2} .

  In addition, as other exposure light sources, ultrahigh pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser light sources, and the like can be used.

~ Exposure process using laser light source ~
In the exposure method using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength range of 300 nm to 410 nm, and more preferably a wavelength of 300 nm to 360 nm. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. . The pattern exposure, from the viewpoint of ^{productivity,} preferably in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable.

  There are no particular restrictions on the exposure apparatus, but commercially available devices include Callisto (buoy technology), EGIS (buoy technology), DF2200G (Dainippon Screen). Can be used. Further, devices other than those described above are also preferably used.

-Development process-
Subsequently, the colored layer after exposure is developed with a developer. Thereby, a colored pattern can be formed. As long as the developing solution dissolves the uncured portion of the colored layer and does not dissolve the cured portion, a combination of various organic solvents or an alkaline aqueous solution can be used. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 10-13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene and the like can be mentioned.
The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 20 ° C to 30 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.
Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water.

  In the method for producing a color filter of the present invention, post-exposure by ultraviolet irradiation may be performed on a colored pattern (pixel) formed using a colored curable composition.

-Post bake process-
It is preferable to further heat-treat the colored pattern after development or the colored pattern subjected to post-exposure by ultraviolet irradiation as described above. By heating the formed color pattern (so-called post-bake process), the color pattern can be further cured. This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having a plurality of hue pixels, the above colored layer forming step, exposing step, developing step, and post-baking step may be repeated according to the desired number of colors.
In addition, every time the formation, exposure, and development of a single color layer are completed (for each color), the above-described post-baking step may be performed, or the formation, exposure, and development of all the colored layers having a desired number of colors. After the process is completed, the post-baking process may be performed collectively.

(Manufacturing method of color filter for COA type liquid crystal display device)
In the color filter for a COA type liquid crystal display device, first, the colored curable composition of the present invention containing a colorant is applied onto a TFT substrate to form a coating film of the colored curable composition. The coating film is subjected to pattern exposure, alkali development, post-baking treatment, and the like to form each pixel, and a transparent electrode (ITO) film is formed on each pixel by sputtering. Next, a positive photoresist coating film is formed, pattern exposure and development are performed on the photoresist film, and necessary ITO is etched to form a pixel electrode pattern. Thereafter, the photoresist film remaining on the pixel electrode pattern is removed with a stripping solution, whereby a COA type color filter for a liquid crystal display device can be manufactured.

  The coating film of the colored curable composition can be formed by applying the colored curable composition directly on the substrate or by another coating method such as spin coating, slit coating, casting coating, roll coating, and inkjet. It can be performed by applying through a layer and drying (pre-baking). The colored curable composition applied on the substrate can be dried (pre-baked) by heating it at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven or the like. In recent years, since the substrate has been increased in size, slit coating is effective as a method for forming a coating film, and this coating method is becoming common.

The said coating film hardens only the part made into a coloring pattern among coating films by exposure (pattern exposure) through a predetermined mask pattern. Examples of radiation suitable for exposure include ultraviolet rays such as g-line and i-line.
In the case of the negative type, by performing alkali development after the pattern exposure, the uncured uncured portion is eluted in the alkaline aqueous solution, and only the photocured portion remains. As a developer suitable for alkali development, an organic alkali developer that does not damage the underlying circuit or the like is desirable. Examples of the organic alkali developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0]. An organic alkaline compound such as -7-undecene diluted with pure water so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass can be used. . When a developer composed of such an organic alkaline aqueous solution is used, the developer is generally washed (rinsed) with pure water after development.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

After the alkali development treatment, excess developer is washed away and dried, followed by heat treatment (post-bake). Post-baking is a heat treatment after development for complete curing, and the heat-curing treatment is usually performed at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C. The post-baking treatment can be performed by heating using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the temperature of the coating film after development is in the above-described condition. it can. The post-bake treatment can be performed either continuously or batchwise.
In this way, a color that is a patterned cured film composed of pixels of a plurality of colors by sequentially repeating the above-described steps of forming RGB colored patterns in sequence using three color curable compositions of RGB. A filter can be formed.

(How to use the color filter for COA type liquid crystal display)
The color filter formed by the above method is used in a COA type liquid crystal display device as follows. First, a transparent electrode (ITO) film is formed on the color filter pixels by sputtering, and a positive photoresist film having etching resistance is further formed thereon. Then, after pattern exposure and development, unnecessary ITO is etched with chemicals such as hydrofluoric acid to form pixel electrodes. For pattern exposure, development, and etching, generally known methods can be used without limitation.
Next, the positive resist remaining on the formed pixel electrode is quickly stripped and removed with a stripping solution. There is no restriction | limiting in particular as stripping solution, A conventionally well-known stripping solution can be used. For example, various publications disclosed in JP-A-51-72503, JP-A-57-84456, JP-A-6-222573, etc., and U.S. Pat. No. 4,165,294 and European Patent No. 0119337. Organic solvents can be used. A typical stripping solution includes a mixed solvent of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO). Further, by using an organic solvent heated to 60 ° C. or higher as the stripping solution, the stripping process can be shortened, and further, there can be no problem of development residue. Since the colored curable composition in the present invention is also excellent in peeling liquid resistance, even when an organic solvent heated to 60 ° C. or higher is used, the color filter coating film peels off, swells or expands. There is no such thing, and the resist film can be removed.

The color filter of the present invention has a structure as disclosed in FIG. 1 of JP-A-9-31347 and is used for various display devices such as a TFT liquid crystal display device.
The color filter obtained as described above is suitable for a COA type image display device because it can be easily aligned and can increase the aperture ratio. In addition, since the color filter forms pixels using the colored curable composition of the present invention, the color filter has high resistance to stripping liquid, and therefore has a high yield rate and high production efficiency. In addition, the heat discoloration, low dielectric constant, film thickness uniformity, resolution, voltage holding ratio, light resistance, etc. that are usually required for color filters are also good.

The structure of the color filter was formed by the colored curable composition of the present invention in addition to the form having only one layer of the pixel formed by the colored curable composition of the present invention between the substrate and the pixel electrode. A mode having two layers of a pixel and a pixel protective film formed on the film of the pixel may be employed.
The film thickness of the pixel is preferably 0.3 μm to 5.0 μm, and more preferably 0.5 μm to 3.5 μm. A thicker pixel can achieve higher chromaticity, but the resolution of the contact hole is deteriorated, so that a balance is necessary.
The film thickness of the pixel protective film is preferably 0.2 μm to 5.0 μm, and more preferably 0.2 μm to 3.0 μm. The pixel protective film can flatten the unevenness of the underlying pixel, and the surface thereof is preferably smooth.

<< Display device >>
The display device of the present invention includes the color filter of the present invention that is excellent in luminance and contrast.
Specifically, the display device of the present invention includes a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display for a portable terminal such as a mobile phone. And display devices such as devices, digital camera display devices, and car navigation display devices. Among these, a color display device is particularly suitable as an object to which the color filter of the present invention is applied.
When the color filter of the present invention is used in an organic EL display device, a liquid crystal display device, or the like, it is possible to display an image with high luminance and excellent spectral characteristics and contrast.

[Liquid Crystal Display]
A liquid crystal display device using the color filter of the present invention will be described. For the definition of organic EL display devices and liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho (issued in 1989) ”. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”.

  The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. can do. Further, as described above, the color filter of the present invention can also be used for a COA type liquid crystal display device.

  When the color filter of the present invention is used in a liquid crystal display device, high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, but further, red, green, and blue LED light sources (RGB) -LED) as a backlight can provide a liquid crystal display device with high luminance, high color purity, and good color reproducibility.

[Method for manufacturing liquid crystal display device]
Examples of the most suitable COA type image display device (hereinafter also simply referred to as “COA”) are shown below for application of a color filter formed using the colored curable composition of the present invention.
A normal color filter is provided on a glass substrate and bonded to a TFT substrate. On the other hand, the COA technique forms a color filter directly on a TFT substrate, and it is necessary to consider the following points (i) to (iii) as compared with a normal color filter material.
(I) Low dielectric constant Since the pixel electrode is directly provided on the TFT in the COA, the voltage is directly applied to the color filter. Therefore, the color filter material is required to be a low dielectric constant material.
(Ii) Contact hole In the COA, the ITO wiring of the pixel electrode needs to be connected to the TFT provided thereunder. For this reason, it is required that the contact hole be reliably formed during development.
(Iii) Resistance to stripping solution In COA, electrode formation is essential for each pixel. The electrodes are formed by sputtering ITO on the pixels, patterning and etching wiring with a positive resist, and then removing the remaining positive resist with a high-temperature stripping solution, usually about 80 ° C. For this reason, the COA is required to have a low swelling rate so that the color filter or the like is not attacked by the stripping solution, and is swollen by the stripping solution so that the ITO cannot follow and disconnect.

  On the other hand, when a color filter is manufactured on a TFT substrate, the appearance of defective products in the color filter manufacturing process includes defective products including the TFT substrate, which is very risky. However, in recent years, as LCDs have become larger as represented by liquid crystal TVs, the size of the production substrate has also increased year by year. Furthermore, since the injection time of liquid crystal becomes long, the liquid crystal injection method is changing to the dropping method. As described above, with the increase in the size of the substrate and the application of the liquid crystal dropping method, when the color filter and the TFT substrate are bonded, the alignment accuracy between the color filter pixel and the TFT becomes severe. Therefore, it is becoming very difficult to correct the positional deviation between the central portion and the peripheral portion of the substrate.

  In this respect, since the COA is provided with pixels directly on the TFT, there is no fear of positional deviation, and a substrate on which ITO is sputtered may be prepared as the counter substrate sandwiching the liquid crystal. For this reason, the necessity of alignment becomes about the position of the sealing agent, and the working efficiency is dramatically improved. As described above, since the COA technology does not require alignment accuracy (it is gradual), the line width of the black matrix can be made very narrow, the aperture ratio can be increased, and the power consumption of the backlight can be increased. There is a merit that can be kept low. In this way, various studies have been made on COA, which may become an essential technology for future LCD large-sized substrates. However, as described above, the risk of producing a color filter on the TFT and the color filter material that can meet the requirements (i) to (iii) are not provided, and therefore, the adoption is advanced. The current situation was not.

In view of the above, the colored curable composition of the present invention can solve the problems caused by the above-mentioned color filter material for COA, and the usage method thereof can be properly used depending on the purpose.
That is, the most desirable method is a method for producing a color filter using the colored curable composition of the present invention containing a colorant.

  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” and “%” are based on mass.

-Preparation of dispersion composition-
[Preparation of Dispersion Compositions 1-22, 29-30]
(Preparation of pigment)
Commercially available C.I. I. Pigment Blue 15: 6 (trade name: FASTOGEN BLUE EP193, manufactured by DIC Corporation) 100 parts, 50 parts of the dyes listed in Table 1 below, 400 parts of sodium chloride, and 140 parts of diethylene glycol, a table-type kneader ( (Made by Irie Shokai Co., Ltd.) and kneaded for 10 hours. Next, this kneaded product was stirred and mixed with water using a dissolver (manufactured by Nippon Seiki Seisakusho), and then filtration and washing were repeated to remove sodium chloride and the solvent to obtain a water cake of a coloring material. Thereafter, the water cake was dried in an oven at 80 ° C. for 6 hours. I. A mixed color material of Pigment Blue 15: 6 and a dye was obtained.

(Coarse dispersion)
It is obtained after mixing 150 parts of the above-mentioned mixed color material, the alkali-soluble resin of the type and number of parts described in Table 1, 10 parts of pigment derivative (I), and 220 parts of solvent (propylene glycol monomethyl ether acetate). The mixture was dispersed using Eiger mill (Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.8 mm.

(Precise dispersion)
The coarsely dispersed pigment dispersion was taken out from the Eiger mill, and 30 parts of a solvent (propylene glycol monomethyl ether acetate) was added to the dispersion 100 and mixed. The obtained mixture was dispersed using an Eiger mill (same as above) and zirconia beads having a diameter of 0.1 mm.

(Density adjustment)
The pigment dispersion after the above precision dispersion was taken out from the Eiger mill and diluted by adding propylene glycol monomethyl ether acetate so that the pigment concentration was 10% by mass to prepare dispersion compositions 1-22, 29-30.

[Preparation of Dispersion Composition 23]
(Preparation of pigment)
Commercially available C.I. I. Pigment Blue 15: 6 (trade name: FASTOGEN BLUE EP193, manufactured by DIC Corporation) 100 parts, 50 parts of the dyes listed in Table 1 below, 400 parts of sodium chloride, and 140 parts of diethylene glycol, a table-type kneader ( (Made by Irie Shokai Co., Ltd.) and kneaded for 10 hours. Next, this kneaded product was stirred and mixed with water using a dissolver (manufactured by Nippon Seiki Seisakusho), and then filtration and washing were repeated to remove sodium chloride and the solvent to obtain a water cake of a coloring material. Thereafter, the water cake was dried in an oven at 80 ° C. for 6 hours. I. A mixed color material of Pigment Blue 15: 6 and a dye was obtained.

(Coarse dispersion)
After mixing 150 parts of the above-mentioned mixed color material, 10 parts of pigment derivative (I), and 220 parts of solvent (propylene glycol monomethyl ether acetate), the resulting mixture was added to Eiger Mill (Eiger Japan Co., Ltd.) And zirconia beads having a diameter of 0.8 mm.

(Precise dispersion)
The pigment dispersion after the coarse dispersion was taken out from the Eiger mill, and 30 parts of propylene glycol monomethyl ether acetate was added to the dispersion 100 and mixed. The obtained mixture was dispersed using an Eiger mill (same as above) and zirconia beads having a diameter of 0.1 mm.

(Density adjustment)
The pigment dispersion after the precision dispersion was taken out from the Eiger mill, diluted with propylene glycol monomethyl ether acetate so that the pigment concentration was 10% by mass, and a dispersion composition 23 was prepared.

-Preparation of dispersion compositions 24-28-
(Miniaturization of pigment)
Commercially available C.I. I. Pigment Blue 15: 6 (trade name: FASTOGEN BLUE EP193, manufactured by DIC Corporation) 100 parts, 400 parts of sodium chloride, and 140 parts of diethylene glycol were charged into a table type kneader (manufactured by Irie Shokai Co., Ltd.), 10 Kneaded for hours. Next, this kneaded product was stirred and mixed with water using a dissolver (manufactured by Nippon Seiki Seisakusho), and then filtration and washing were repeated to remove sodium chloride and the solvent to obtain a water cake of a coloring material. Thereafter, the water cake was dried in an oven at 80 ° C. for 6 hours. I. Pigment Blue 15: 6 refined pigment was obtained.

(Coarse dispersion)
It was obtained after mixing 100 parts of the above-mentioned refined pigment, 120 parts of alkali-soluble resin described in Table 1 below, 10 parts of pigment derivative (I), and 220 parts of solvent (propylene glycol monomethyl ether acetate). The mixture was dispersed using Eiger mill (Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.8 mm.

(Precise dispersion)
The pigment dispersion after the coarse dispersion was taken out from the Eiger mill, and 30 parts of propylene glycol monomethyl ether acetate was added to the dispersion 100 and mixed. The obtained mixture was dispersed using an Eiger mill (same as above) and zirconia beads having a diameter of 0.1 mm.

(Density adjustment)
The pigment dispersion after the precision dispersion was taken out from the Eiger mill, diluted with propylene glycol monomethyl ether acetate so that the pigment concentration was 10% by mass, and dispersion compositions 24-28 were prepared.

  The structures of Dye 1 (A-1), Dye 2 (A-2), and Dye 3 (A-3) shown in Table 1 are shown below.

-Synthesis of pigment derivative (I)-
The pigment derivatives (I) listed in Table 1 were synthesized according to the method described in paragraph 0056 of JP2003-253078. CuPc in the following structural formula represents a copper phthalocyanine residue.

Below, the detail of each resin of the said Table 1 is shown.
Resin 1-1 and Resin B are alkali-soluble resins represented by the following structure.
Further, the other resin is an alkali-soluble resin obtained by changing the constituent component species (monomer species) shown in Table 2 or the ratio thereof in the resin 1-1 represented by the following structure.
In addition, the resin 1-1 to the resin 5 are specific alkali-soluble resins in the present invention including the structure derived from the general formula (i) as the component (b2), and the resins 6 to 9 do not include the component (b2). Comparative resin. Resin B is a specific alkali-soluble resin containing a structure derived from general formula (ii) as component (b2).

m: n: p: q = 30: 10: 35: 25 (mass ratio) Mw: 9500

<Example 1>
-Preparation of colored curable composition-
The following components were mixed and dissolved to prepare a colored curable composition.
Organic solvent 1 (propylene glycol monomethyl ether acetate) 5.1g
・ Organic solvent 2 (diethylene glycol ethyl methyl ether) 17.1 g
Polymerizable compound 1 (trade name: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 4.0 g
Polymerizable compound 2 (trade name: Aronix TO-2349, manufactured by Toa Gosei Co., Ltd.)
1.3g
・ Polymerization inhibitor (p-methoxyphenol) 0.003g
Photopolymerization initiator 1 (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone) 0.5 g
・ UV absorber (structure below) 0.32g
・ Polyfunctional thiol compound (the following structure) 0.35g
-Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.16 g
-Fluorosurfactant (trade name: Megafac F-554, 0.2% propylene glycol monomethyl ether acetate solution, manufactured by DIC Corporation) 8.0 g
-Dispersion composition 1 63.2g

  Below, the structure of the ultraviolet absorber used in preparation of the said colored curable composition and a polyfunctional thiol compound is shown.

<Examples 2 to 24, Comparative Examples 1 to 5, and Comparative Example 11>
-Preparation of colored curable composition-
In Example 1, according to Table 3, the colored curable composition of each Example and each comparative example was prepared like Example 1 except having changed the kind of dispersion composition and photoinitiator. did.
However, in Table 3, the photopolymerization initiator 2 is “(2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one)”.

<Comparative Examples 6 to 10>
-Preparation of colored curable composition-
In Example 1, according to Table 3, the type of the dispersion composition was changed to a dispersion composition containing no dye, and the same amount of dye 1 (A-1) as in Example 1 was used when preparing the colored curable composition. In addition, the colored curable composition of each comparative example was prepared like Example 1 except mixing and dissolving.

  In Table 3, the difference in the structure of the colored curable composition of Examples 1-24 and Comparative Examples 1-11 is shown roughly.

-Evaluation-
The dielectric constant, release liquid resistance, chemical resistance, and heat resistance of the colored curable composition prepared above were evaluated by the following methods. The evaluation results are shown in Table 4 below.

(1) Relative permittivity a) On a chromium-coated glass substrate (length of one side: 75 mm, chromium film thickness: 0.3 μm), the film thickness after curing (after post-baking) becomes 3.0 μm. Using the spin coater with the rotational speed adjusted as described above, the colored curable compositions of Examples 1 to 24 and Comparative Examples 1 to 11 prepared above were respectively applied.
b) Next, the chromium-coated glass substrate on which the coating film was formed was pre-baked on a hot plate at 100 ° C. for 120 seconds, and the solvent was dried.
c) After pre-baking, the coating film was irradiated with light at an exposure amount of 200 mJ / cm ² using a 2.5 kw ultra-high pressure mercury lamp.
d) Next, the chromium-coated glass substrate on which the coating film was formed was heated and cured (post-baked) at 220 ° C. for 60 minutes with a hot-air circulation dryer to prepare a test piece.
e) After post-baking, the coating film at one corner of the test piece was scraped to expose the chromium surface.
f) Next, a silver paste was spin-coated on the back surface of the test piece and air-dried. Then, the chromium exposed surface on the front surface and the silver paste coated surface on the back surface were electrically connected (connected) with the silver paste.

  g) After drying, using a vacuum vapor deposition apparatus (trade name: Ion Sputter E1030, manufactured by Hitachi, Ltd.), using a Pt / Pd target material, as shown in FIG. The main electrode 2 (inner circle) and the guard electrode 3 (outer circle) having a deposition thickness of about 50 nm were prepared on the surface). On the substrate 1, the chromium surface 4 shaved in e) is exposed.

h) After the electrode was prepared, the thickness of the coating film on the part without the electrode was measured with a stylus type surface shape measuring instrument (trade name: DEKTAK3, manufactured by ULVAC, Inc.).
i) Next, a dielectric test fixture 16451B and an electrode were attached to a capacitance measuring instrument (precision impedance analyzer 4294A, manufactured by Agilent Technologies), and the test piece in g) above was further attached, and 1 kHz, 0.5 V The relative dielectric constant ε ′ when an alternating voltage of 1 was applied was measured and evaluated based on the following criteria.

(Evaluation criteria)
A: relative dielectric constant ε ′ <3.0
B: Relative permittivity ε ′ 3.0 to 5.0
C: relative dielectric constant ε ′> 5.0

(2) Stripping solution resistance The film thickness of the test piece was measured by the following procedures a) to e) to calculate the swelling ratio, and the calculated value was used as an index for evaluating the stripping solution resistance. However, those with poor stripping solution resistance cannot be measured for film thickness because the coating film dissolves in the stripping solution or peels off from the substrate when immersed in the stripping solution. Such a thing was evaluated as "C".

a) The film thickness (FT ₀ ) of the test piece obtained in d) in the above (1) relative dielectric constant was measured.
b) After measurement, a mixture of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (MEA / DMSO = 7/3 mass ratio) was used as the stripping solution, and the above test piece was stripped at 80 ° C. For 120 seconds.
c) Fill the bat with a solution of MEA / DMSO = 7/3, immerse the test piece after immersion in b) above, and then stylus type surface shape measuring instrument (trade name: DEKTAK3, ULVAC, Inc.) The test piece with the surface covered with the stripping solution was placed on the test strip support, and the coating thickness (FT ₁ ) was measured (measurement of the film thickness in the swollen state with the stripping solution).

d) After filling another bat with pure water, immersing the test piece swollen in the above c) and allowing it to stand overnight to replace the stripping solution and water contained in the coating film, the test piece was placed at 200 ° C. for 30 minutes. After drying for a minute, the coating thickness (FT ₂ ) was measured again.
e) Using FT ₀ , FT ₁ , and FT ₂ measured as described above, the swelling rate and film reduction rate of the test piece were calculated according to the following formulas, and the stripping solution resistance was evaluated based on the following criteria. Since (FT ₁ -FT ₀ ) measures the apparent swelling due to the stripping solution, it is corrected by the film loss (FT ₂ -FT ₀ ) eroded by the stripping solution, and the true swelling rate is calculated. did.
True swelling ratio (%) = 100 × (FT ₁ −FT ₂ ) / F ₀
Film reduction rate (%) = 100 × (FT ₂ −FT ₀ ) / F ₀

(Evaluation criteria)
A: True swelling rate ≦ 40%, film reduction rate ≦ 5%, and good stripping solution resistance.
B: True swelling rate ≦ 40%, film reduction rate> 5%, and resistance to stripping solution is within an allowable range.
C: The coating film is dissolved or peeled off, and the stripping solution resistance is inferior.

(3) Chemical resistance-Formation of colored curable composition layer (colored layer)-
After applying the colored curable compositions of Examples 1 to 24 and Comparative Examples 1 to 11 prepared above on a glass (# 1737, Corning) substrate by a spin coat method, the substrate is dried at room temperature for 30 minutes. Thus, the volatile component was volatilized to form the colored layer A. The colored layer A was irradiated with i rays (wavelength 365 nm) to form a latent image. An ultra-high pressure mercury lamp was used as the i-line light source, and it was irradiated as parallel light. At this time, the irradiation light quantity was 40 mJ / cm ² . Next, the colored layer on which the latent image was formed was developed with an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%) at 26 ° C. for 45 seconds, and then rinsed with running water for 20 seconds. And dried with a spray to obtain a fine line pattern image. The obtained fine line pattern image was post-baked at 230 ° C. for 20 minutes to obtain a colored layer (colored cured film) B having a thickness of 2 μm.

The transmission spectrum of the colored layer B obtained above was measured using a spectrophotometer (instant multiphotometry system MCPD-3700, manufactured by Otsuka Electronics Co., Ltd.). Moreover, about the colored layer B obtained above, the chemical-resistance test was done in the following procedures a) -c), and the transmission spectrum after a test was measured similarly. Then, the change in chromaticity (ΔE ^* ab) before and after the treatment was determined from the transmission spectrum. Here, ΔE ^* ab means a color difference in the L ^* a ^* b ^* color system. The chromaticity change (ΔE ^* ab) was used as an index for evaluating chemical resistance.

a) An ITO film having a thickness of 100 nm (conductive) is formed by sputtering ITO (Indium Tin Oxide) on the colored layer B using a sputtering apparatus under film forming conditions (200 mm / min, sputtering temperature: 90 ° C.). Film pattern) was formed, and a colored layer C with ITO was produced.
b) The colored layer C obtained above was immersed in N-methylpyrrolidone at 25 ° C. for 5 minutes.
c) Next, the colored layer C was baked for 15 minutes on a hot plate at 240 ° C. to obtain a colored layer B after the test.

(Evaluation criteria)
The chromaticity change ΔE ^* ab is preferably smaller in numerical value, and indicates that the chromaticity change due to chemicals is small.
Chromaticity change ΔE ^* ab ≦ 3.0: Good chemical resistance.
Chromaticity change ΔE ^* ab> 3.0: Chemical resistance is poor.

(4) Heat resistance The transmission spectrum of the colored layer B obtained above was measured using a spectrophotometer (instant multiphotometry system MCPD-3700, manufactured by Otsuka Electronics Co., Ltd.). Further, the colored layer B obtained above was subjected to additional post-baking treatment at 230 ° C. for 40 minutes, and the transmission spectrum after the treatment was measured in the same manner. Then, the chromaticity coordinate x value, y value, and Y value in the CIE 1931 color system are obtained from the transmission spectra before and after the above processing, and the Y value (luminance) at (x, y) = (0.138, 0.085). It was confirmed. Furthermore, the change in chromaticity (ΔE ^* ab) before and after the treatment was determined. Here, ΔE ^* ab means a color difference in the L ^* a ^* b ^* color system. The luminance and chromaticity change (ΔE ^* ab) was used as an index for evaluating heat resistance.

(Evaluation criteria)
The luminance can be said to be excellent when the Y value at (x, y) = (0.138, 0.085) is high. And it is preferable that the luminance has a large numerical value, and the higher the numerical value, the smaller the decrease in luminance due to heating.
Luminance ≧ 10.10 or more: Good luminance.
Luminance << 10.10: The luminance is inferior.

The chromaticity change ΔE ^* ab is preferably smaller in numerical value and represents that the change in chromaticity due to heating is small.
Chromaticity change ΔE ^* ab ≦ 3.0: Good heat resistance.
Chromaticity change ΔE ^* ab> 3.0: Heat resistance is poor.

(5) Dye adsorption rate About the dispersion compositions 1-30 prepared above, the ratio (dye adsorption rate) of the dye adsorb | sucking to the surface of an organic pigment was calculated | required with the following method.
The dispersion compositions 1 to 30 were centrifuged using an ultracentrifuge (Hitachi Koki Co., Ltd. 50000 rpm) to obtain a supernatant. The amount of the dye in the obtained supernatant was measured by HPLC, and the following formula Based on the above, the dye adsorption rate (%) was calculated.
Dye adsorption rate (%) = [1- (Amount of dye in supernatant (g) / Prescription amount of dye in dispersion composition (g))] × 100

As shown in Table 4, according to the colored curable composition of the present invention (Examples 1 to 24), a change in chromaticity due to heating hardly occurs, and a high-intensity colored cured film can be formed. It was. In addition, according to the colored curable composition of the present invention (Examples 1 to 24), it was possible to form a colored cured film excellent in chemical resistance, in which a change in chromaticity due to chemicals hardly occurs. Furthermore, the colored cured film formed using the colored curable composition of the present invention (Examples 1 to 24) had a low relative dielectric constant and high stripping solution resistance.
The colored curable composition (Comparative Examples 1 to 15) not containing the specific alkali-soluble resin has a lower dye adsorption rate than the colored curable composition of the present invention (Examples 1 to 24) containing the resin. Showed a tendency to become.
In a colored curable composition (Comparative Examples 6 to 10) prepared by dispersing an organic pigment in a solvent under the condition where no dye was present, it was confirmed that the blended dye was not adsorbed on the surface of the organic pigment.

1 Substrate 2 Main electrode 3 Guard electrode 4 Chrome surface

Claims (14)

At least one of an organic pigment, a dye containing a mother skeleton different from the organic pigment, adsorbed on the surface of the organic pigment, a structural unit (b1) having a carboxyl group in a side chain, and the structural unit (b1) An alkali-soluble resin containing a structural unit (b2) in which at least one compound selected from a compound represented by the following general formula (i) and a compound represented by the following general formula (ii) is added to a part; And a curable compound.

In general formula (i) and general formula (ii), Z represents a hydrogen atom or a methyl group.   The colored photosensitive composition according to claim 1, wherein the alkali-soluble resin is a resin further containing a structural unit (b3) having a polycyclic alicyclic alkyl group in a side chain.   The colored photosensitive composition according to claim 2, wherein the polycyclic alicyclic alkyl group is a tricyclodecanyl group or a dicyclopentadienyl group.   The colored photosensitive composition according to any one of claims 1 to 3, wherein the content of the structural unit (b2) in the alkali-soluble resin is 0.1 mass% or more and 70 mass% or less.   The colored photosensitivity according to any one of claims 1 to 4, wherein the content of the alkali-soluble resin is 1% by mass or more and 70% by mass or less based on the total solid content of the colored photosensitive composition. Composition.   The colored curable composition according to any one of claims 1 to 5, wherein the organic pigment is a phthalocyanine pigment. The colored curable composition according to any one of claims 1 to 6, wherein the dye is a complex in which a compound represented by the following general formula (I) is coordinated to a metal atom or a metal compound.

(In general formula (I), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ is a hydrogen atom, Represents a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.)   Furthermore, the colored curable composition of any one of Claims 1-7 containing a photoinitiator. At least one of an organic pigment, a dye containing a mother skeleton different from the organic pigment, adsorbed on the surface of the organic pigment, a structural unit (b1) having a carboxyl group in a side chain, and the structural unit (b1) An alkali-soluble resin containing a structural unit (b2) in which at least one compound selected from a compound represented by the following general formula (i) and a compound represented by the following general formula (ii) is added to a part; A method for producing a colored curable composition comprising mixing an organic compound and a solvent through a process of dispersing the organic pigment in the solvent in the presence of at least the dye.

In general formula (i) and general formula (ii), Z represents a hydrogen atom or a methyl group.   The colored curable composition according to claim 9, wherein in the step, at least the organic pigment and the dye are kneaded together with a solvent, and the obtained kneaded material is further mixed with a solvent to disperse the organic pigment. Production method.   A color filter formed using the colored curable composition according to any one of claims 1 to 8 or the colored curable composition obtained by the production method according to claim 9 or 10. .   The colored curable composition according to any one of claims 1 to 8 or the colored curable composition obtained by the production method according to claim 9 or 10 is applied on a support. A color filter comprising: a colored layer forming step for forming a colored layer; an exposure step for exposing the formed colored layer in a pattern; and a developing step for developing the colored layer after exposure to form a colored pattern. Production method.   A display device comprising the color filter according to claim 11 or the color filter obtained by the production method according to claim 12.   The colored curable composition according to any one of claims 1 to 8, or the production method according to claim 9 or 10, on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. A liquid crystal display device comprising a color filter having pixels formed of the colored curable composition obtained by the above.