JP2011016974A - Colored curable composition, color resist, inkjet ink, color filter and method for producing the same, solid-state image pickup device using the same, image display, liquid crystal display and organic electroluminescence display using the same, and colorant compound and tautomer thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable composition, which has excellent color purity, heat resistance and light resistance and which can be formed into a thinner layer: a color resist having favorable pattern formability; inkjet ink having excellent jetting stability; and a color filter having a favorable pattern shape and a method for producing a color filter using the composition.SOLUTION: The colored curable composition includes: at least one kind selected from the group consisting of a compound expressed by general formula (1) and a tautomer thereof; and at least one polymerizable compound. In general formula (1), R, R, R, R, Rand Reach independently represents a hydrogen atom or a monovalent substituent.

Description

  The present invention relates to a color curable composition suitable for a color resist used for forming a colored pixel by a photolithographic method, an inkjet ink used for forming a colored pixel by an inkjet method, a color filter using the same, and a method for producing the same, and The present invention relates to a solid-state imaging device using a color filter, an image display device, a liquid crystal display, an organic EL display, a dye compound, and a tautomer thereof.

In recent years, with the development of personal computers, particularly large-screen liquid crystal televisions, the demand for liquid crystal displays (LCD), especially color liquid crystal displays, has been increasing. The spread of organic EL displays is also awaited due to the demand for higher image quality.
On the other hand, the demand for solid-state imaging devices such as CCD image sensors has greatly increased due to the spread of digital cameras and camera-equipped mobile phones. Color filters are used as key devices for these displays and optical elements, and the demand for cost reduction is increasing along with the demand for higher image quality. Such a color filter usually has a coloring pattern of three primary colors of red (R), green (G), and blue (B), and colors light passing therethrough in an image display device or a solid-state imaging device. Or plays the role of decomposing into the three primary colors.

  The colorant used in the color filter is required to have the following properties in common. In other words, it has favorable light absorption characteristics in terms of color reproducibility, optical scattering such as light scattering that causes a decrease in contrast of a liquid crystal display, and unevenness in optical density that causes color unevenness and roughness of a solid-state imaging device. There is a need for it to be excellent in toughness under the environmental conditions in use, for example, heat resistance, light resistance, wet heat resistance, etc., to have a large molar extinction coefficient and to be capable of being thinned.

  A pigment dispersion method is used as one of methods for producing a color filter used for a solid-state imaging device, a liquid crystal display, an organic EL display, and the like. A method for producing a color filter by a photolithography method or an inkjet method by a pigment dispersion method is stable to light and heat because a pigment is used.

  In order to produce a color filter by a photolithographic method, a radiation-sensitive composition is applied on a substrate with a spin coater, slit coater, roll coater, etc., dried to form a coating film, and the coating film is subjected to pattern exposure and development. By doing so, a colored pixel is obtained. A color filter can be produced by repeating this operation for the number of hues. Since the patterning is performed by light, sufficient positional accuracy can be secured, and the method is widely used as a method suitable for producing a high-definition color filter having a large screen used for a liquid crystal display, an organic EL display or the like.

  In a color filter for a solid-state imaging device, exposure is performed through a fine pattern mask, followed by development with an alkaline solution, and an unexposed portion is dissolved in an alkaline developer to form a fine pattern. It is difficult to adjust the solubility (developability) of the exposed area.

In recent years, there has been a demand for higher definition color filters for solid-state imaging devices, and the conventional pigment dispersion method further improves resolution due to problems such as color unevenness due to coarse pigment particles. In order to achieve high definition, it is becoming difficult to apply a photolithography method using a pigment dispersion method.
On the other hand, in liquid crystal displays, organic EL displays, etc., the color filter manufactured by the photolithography method using the pigment dispersion method is excellent in light resistance and heat resistance, but the contrast is reduced due to light scattering by the pigment particles, haze. The problem of increase is still a major issue.

  In addition, as described above, in the photolithographic method, it is necessary to repeat the steps of applying the radiation-sensitive composition, drying, pattern exposure, and development as many times as the number of hues. Therefore, there is a problem that the yield decreases. In particular, due to the increasing demand for cost reduction of liquid crystal displays, the demand for cost reduction for color filters with high specific gravity is increasing, and there is an increasing demand for more highly productive color filter manufacturing methods. Yes.

  As a method of manufacturing a color filter that solves the problem of the photolithography method, a method of forming a colored layer (color pixel) by ejecting colored ink by an inkjet method has been proposed (see Patent Documents 1 and 2).

  The ink jet method is a recording method in which characters and images are obtained by ejecting and adhering ink droplets directly from a very fine nozzle to a recording member. The ink jet method has an advantage that a color filter having a large area can be manufactured with high productivity by sequentially moving the ink jet head, and the operability is low with low noise. Ink jet ink using a pigment dispersion method is used for manufacturing a color filter by such an ink jet method. As an inkjet ink using such a pigment dispersion method, for example, for a color filter containing a binder component, a pigment, and a solvent having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less. An inkjet ink has been proposed (see Patent Document 3).

  When ink jet ink using the pigment dispersion method is used for manufacturing a color filter, nozzle clogging due to pigment aggregation frequently occurs, which is not preferable from the viewpoint of ejection stability. Further, the aggregated pigment deteriorates the ink discharge state recovery function by the discharge recovery operation such as wiping and purging. In addition, at the time of wiping, the nozzle surface may be rubbed by the agglomerated pigment, and the ink ejection direction may be bent.

  When dyes are used instead of the pigment dispersion method, high resolution can be achieved by solving the problem of color unevenness and roughness in the color filters for solid-state image sensors, while optical properties such as contrast and haze are achieved in liquid crystal displays and organic EL displays. Each improvement is expected. Ink jet methods using dyes generally have high ejection stability, and it is expected that the ink ejection state can be easily recovered by wiping or purging even when nozzle clogging occurs due to an increase in ink viscosity.

For the reasons described above, the use of a dye as a coloring material has been studied (for example, see Patent Document 4). However, the colored curable composition containing a dye has the following new problems.
(1) Dyes are generally inferior in light resistance and heat resistance compared to pigments. In particular, there is a problem that optical characteristics change due to a high-temperature process during the formation of ITO (indium tin oxide), which is frequently used as an electrode for liquid crystal displays and the like.
(2) Since dyes tend to suppress radical polymerization reaction, it is difficult to design a colored curable composition in a system using radical polymerization as a curing means.
Especially in photolithography,
(3) Since ordinary dyes have low solubility in an alkaline aqueous solution or an organic solvent (hereinafter also simply referred to as a solvent), it is difficult to obtain a colored curable composition having a desired spectrum.
(4) The dye often exhibits interaction with other components in the colored curable composition, and it is difficult to adjust the solubility (developability) of the exposed and unexposed areas.
(5) When the molar extinction coefficient (ε) of the dye is low, a large amount of dye must be added. For that purpose, a polymerizable compound (monomer), a binder, a photopolymerization initiator, etc. in the colored curable composition Other components must be relatively reduced, and the curability of the composition, the heat resistance after curing, the developability, and the like are lowered.

  Because of these problems, it has heretofore been difficult to form a colored pattern which is formed into a fine and thin film for a high-definition color filter and has excellent fastness using a dye. In the case of a color filter for a solid-state image sensor, it is required that the colored layer be a thin film of 1 μm or less. Therefore, in order to obtain a desired absorption, it is necessary to add a large amount of a dye in the curable composition, resulting in the above-mentioned problems.

  On the other hand, in a colored curable composition containing a dye, when heat treatment is carried out after film formation, a phenomenon of color transfer between adjacent colored patterns having different hues or between overlapping layers is likely to occur. It has been pointed out. In addition to color migration, the pattern is easily peeled off in the low exposure area due to sensitivity reduction, and the amount of photosensitive components that contribute to photolithographic properties is relatively reduced. There are also problems such as inability to obtain the shape and color density.

  As a method for solving such a problem, various methods have been proposed in the past, such as selecting the type of initiator and increasing the amount of initiator added (see, for example, Patent Document 4). In addition, a method for producing a color filter is disclosed in which polymerization is performed with the exposure temperature raised by irradiating the colored pattern with light while heating the substrate after forming the colored pattern, thereby increasing the polymerization rate of the system. (For example, refer to Patent Document 5). Furthermore, a method for manufacturing a color filter is disclosed in which light irradiation is performed between the development process and the heat treatment to prevent the shape of the color filter from being deformed (see, for example, Patent Document 6).

JP 59-75205 A JP 2004-339332 A JP 2002-201387 A Japanese Patent Laying-Open No. 2005-316012 Japanese Patent No. 3309514 JP 2006-258916 A

An object of the present invention is to provide a colored curable composition having excellent color purity, heat resistance and light resistance, and capable of being thinned, and color purity and heat resistance used for forming colored pixels by photolithography. To provide an ink-jet ink excellent in discharge stability and color purity, heat resistance and light resistance used for forming colored pixels by an inkjet method And
It is another object of the present invention to provide a color filter excellent in color purity, heat resistance, and light resistance and having a good pattern shape, and a method for manufacturing the color filter.
In addition, it has excellent color purity, heat resistance, and light resistance, high-resolution solid-state imaging device, excellent color purity, heat resistance, light resistance, good color reproducibility, and images such as high-definition liquid crystal displays and organic EL displays It is an object to provide a display device.
Furthermore, this invention makes it a subject to provide the novel pigment compound which is useful for the coloring curable composition for color filters, etc., is excellent in the absorption characteristic, and has a high molar absorption light coefficient, and its tautomer.

As a result of detailed examination of various dyes, the present inventors have found that an azo dye compound having a specific structure has a good hue and a high extinction coefficient, is excellent in fastness such as heat resistance and light resistance, and is organic. Knowledge that it is excellent in solubility in solvents, and that it is possible to develop dyes that are excellent in pattern formation by introducing an alkali-soluble group if necessary (low concentration dependency of alkali developer) Obtained. The present invention has been achieved based on such findings.
Specific means for solving the above-mentioned problems are as follows.

<1> A colored curable composition containing at least one selected from the group consisting of compounds represented by the following general formula (1) and tautomers thereof, and at least one polymerizable compound. object.

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. R ¹¹ and R ¹² , and R ¹⁵ and R ¹⁶ may be independently bonded to each other to form a ring.)

<2> The colored curable composition according to <1>, wherein the general formula (1) is the following general formula (2).

(In General Formula (2), R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁶ , R ³¹ , R ³² , R ³⁴ , R ³⁵ , and R ³⁶ are each independently a hydrogen atom or monovalent substitution. L ¹ represents a divalent linking group, and R ²¹ and R ²² , R ²⁵ and R ²⁶ , R ³¹ and R ³² , and R ³⁵ and R ³⁶ are each independently bonded to each other to form a ring. (It may be formed.)

<3> The colored curable composition according to <1> or <2>, wherein the compound represented by the general formula (1) is a compound including at least one repeating unit represented by the following general formula (P). object.

(In General Formula (P), R ^P1 , R ^P2 and R ^P3 each independently represent a hydrogen atom or a monovalent substituent, and * represents one hydrogen atom removed from General Formula (1). Represents a bond that binds to a residue, and n represents an integer of 1 to 100.)

<4> The colored curable composition according to any one of <1> to <3>, wherein the polymerizable compound is a compound having two or more ethylenically unsaturated groups in the molecule.
<5> A color resist comprising the colored curable composition according to any one of <1> to <4> and used for forming a colored pixel by a photolithography method.

<6> An inkjet ink that includes the colored curable composition according to any one of <1> to <4> and is used for forming colored pixels by an inkjet method.
<7> A color filter using the colored curable composition according to any one of <1> to <4>.
<8> A step of applying a colored curable composition according to any one of <1> to <4> on a support to form a colored layer, and exposing the colored layer through a mask And a step of forming a pattern by development after the exposure.

<9> The method for producing a color filter according to <8>, further including a step of irradiating ultraviolet rays after the step of forming a pattern by the development.
<10> A colored pixel is formed by ejecting the colored curable composition according to any one of <1> to <4> into a recess defined by a partition formed on a substrate by an inkjet method. A method of manufacturing a color filter having a pixel forming step.

<11> A solid-state imaging device comprising the color filter according to <7>.
<12> An image display device comprising the color filter according to <7>.
<13> A liquid crystal display comprising the color filter according to <7>.
<14> An organic EL display comprising the color filter according to <7>.

<15> A dye compound represented by the following general formula (2) and tautomers thereof.

(In General Formula (2), R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁶ , R ³¹ , R ³² , R ³⁴ , R ³⁵ , and R ³⁶ are each independently a hydrogen atom or monovalent substitution. L ¹ represents a divalent linking group, and R ²¹ and R ²² , R ²⁵ and R ²⁶ , R ³¹ and R ³² , and R ³⁵ and R ³⁶ are each independently bonded to each other to form a ring. (It may be formed.)

<16> A dye compound containing at least one repeating unit represented by the following general formula (P) and tautomers thereof.

In the general formula (P), R ^P1 , R ^P2 , and R ^P3 each independently represent a hydrogen atom or a monovalent substituent, and * represents a residue obtained by removing one hydrogen atom from the following general formula (1) Represents a group, and n represents an integer of 1 to 100.

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. R ¹¹ and R ¹² , and R ¹⁵ and R ¹⁶ may be independently bonded to each other to form a ring.)

<17> The dye compound according to <16> and the tautomer thereof, wherein the dye compound has an acid group in a range of 25 mgKOH / g to 200 mgKOH / g.

According to the present invention, it is possible to provide a colored curable composition that is excellent in color purity, heat resistance, light resistance, and capable of being thinned. Also, color purity used for forming colored pixels by a photolithography method, To provide a color resist having excellent heat resistance and light resistance, good pattern formability, color purity used for forming colored pixels by an ink jet method, heat resistance, light resistance, and ink jet ink having excellent ejection stability. it can.
In addition, it is possible to provide a color filter excellent in color purity, heat resistance, and light resistance and having a good pattern shape, and a method for manufacturing the color filter.
In addition, it has excellent color purity, heat resistance, and light resistance, high-resolution solid-state imaging device, excellent color purity, heat resistance, light resistance, good color reproducibility, and images such as high-definition liquid crystal displays and organic EL displays A display device can be provided.
Furthermore, the present invention can provide novel dye compounds that are useful for colored curable compositions for color filters and the like, have excellent absorption characteristics, and have a high molar absorption coefficient and their tautomers.

It is a solution transmission spectrum in the ethyl acetate of the exemplary compound 6 of this invention. It is a spectral characteristic of the color filter produced in Example 1 of this invention. It is the spectrum of the backlight used by the measurement of contrast.

  Below, the coloring curable composition of this invention, a color filter, and the manufacturing method of a color filter are explained in full detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

-Colored curable composition-
The colored curable composition of the present invention comprises, as a colorant, at least one selected from the group consisting of the compound represented by the general formula (1) and tautomers thereof, and a polymerizable compound. contains. The colorant used in the present invention is characterized by containing in the molecule a residue obtained by removing one or more hydrogen atoms from the general formula (1). The colorant of the present invention is at least one selected from the group consisting of the compound represented by the general formula (1) and tautomers thereof, and the compound represented by the general formula (1) includes And a compound containing at least one repeating unit represented by formula (P). If necessary, the compound represented by the general formula (1) and at least one selected from the group consisting of tautomers thereof and the compound containing at least one repeating unit represented by the general formula (P) And may be used in combination.
The colored curable composition of the present invention is characterized by being cured by heat, light, or both, and may be constituted by using other components such as a polymerization initiator, a solvent, a binder, and a crosslinking agent as necessary. can do.
First, the compound represented by the general formula (1) will be described.

<Compound represented by the general formula (1)>
The compound represented by the general formula (1) used in the present invention (hereinafter sometimes referred to as “specific azo dye compound”) will be described in detail.
The specific azo dye compound used in the present invention is an azo dye compound characterized in that the coupling component is aminothiazole and the diazo component is imidazole. Azo dyes having aminothiazole as a coupling component are described in JP-A No. 54-65730 and US Pat. No. 5,789,560 (for example, Exemplified Compound 76), and imidazole as a diazo component. The dyes are disclosed in JP-A-50-130820 and JP-A-55-71754.
In the present invention, when this specific azo dye compound is used as a colored curable composition in a color filter application, it satisfies the characteristics required as a color filter, particularly high resolution, high definition, high color reproduction, and high contrast. Can do.

In General Formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. R ¹¹ and R ¹² , and R ¹⁵ and R ¹⁶ may be independently bonded to each other to form a ring.

In the general formula (1), R ¹¹ , R ¹² , and R ¹⁴ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent is, for example, a halogen atom, an alkyl group having 1 to 30 carbon atoms (in the present application, a saturated aliphatic group including a cycloalkyl group or a bicycloalkyl group), an alkenyl group having 2 to 30 carbon atoms ( In the present application, it means a cycloalkenyl group, an unsaturated aliphatic group having a double bond including a bicycloalkenyl group), an alkynyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 3 to 30 carbon atoms. Heterocyclic group, cyano group, aliphatic oxy group having 1 to 30 carbon atoms, aryloxy group having 6 to 30 carbon atoms, acyloxy group having 2 to 30 carbon atoms, carbamoyloxy group having 1 to 30 carbon atoms, carbon number An aliphatic oxycarbonyloxy group having 2 to 30 carbon atoms, an aryloxycarbonyloxy group having 7 to 30 carbon atoms, an amino group having 0 to 30 carbon atoms (alkylamino group, anilino group and hete A cyclic amino group), an acylamino group having 2 to 30 carbon atoms, an aminocarbonylamino group having 1 to 30 carbon atoms, an aliphatic oxycarbonylamino group having 2 to 30 carbon atoms, and an aryloxycarbonylamino group having 7 to 30 carbon atoms. Group, C 0-30 sulfamoylamino group, C 1-30 alkyl or arylsulfonylamino group, C 1-30 alkylthio group, C 6-30 arylthio group, C 0-30 Sulfamoyl group, alkyl group having 1 to 30 carbon atoms or arylsulfinyl group, alkyl group having 1 to 30 carbon atoms or arylsulfonyl group, acyl group having 2 to 30 carbon atoms, aryloxycarbonyl group having 6 to 30 carbon atoms, carbon number An aliphatic oxycarbonyl group having 2 to 30 carbon atoms, a carbamoyl group having 1 to 30 carbon atoms, and an ant having 3 to 30 carbon atoms Le or heterocyclic azo group, imide group and the like, each group may further have a substituent.

In the general formula (1), R ¹³ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Heterocyclic groups, acyl groups having 2 to 30 carbon atoms, aryloxycarbonyl groups having 7 to 30 carbon atoms, alkoxycarbonyl groups having 2 to 30 carbon atoms, and carbamoyl groups having 1 to 30 carbon atoms. May further have a substituent.
In a preferred embodiment, R ¹³ is a residue of a compound represented by the general formula (1) via a divalent linking group. In this case, a compound having the structure of the general formula (2) described later is obtained.

The monovalent substituents in R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ and the substituents that may be further substituted will be described in detail below.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable.

  The aliphatic group is a linear, branched, or cyclic aliphatic group. As described above, the saturated aliphatic group includes an alkyl group, a cycloalkyl group, and a bicycloalkyl group, and has a substituent. May be. These carbon numbers are preferably 1-30. Examples include methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, benzyl and 2-ethylhexyl. be able to. Here, the cycloalkyl group includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms. Examples include a cyclohexyl group, a cyclopentyl group, and a 4-n-dodecylcyclohexyl group. Examples of the bicycloalkyl group include a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Examples include a bicyclo [1.2.2] heptan-2-yl group and a bicyclo [2.2.2] octan-3-yl group. Further, it includes a tricyclo structure having many ring structures.

  The unsaturated aliphatic group is a linear, branched or cyclic unsaturated aliphatic group, and includes an alkenyl group, a cycloalkenyl group, a bicycloalkenyl group, and an alkynyl group. The alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. As the alkenyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms is preferable. Examples include vinyl group, allyl group, prenyl group, geranyl group, and oleyl group. The cycloalkenyl group is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms. Examples include a 2-cyclopenten-1-yl group and a 2-cyclohexen-1-yl group. The bicycloalkenyl group includes a substituted or unsubstituted bicycloalkenyl group. The bicycloalkenyl group is preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. Examples include a bicyclo [2.2.1] hept-2-en-1-yl group and a bicyclo [2.2.2] oct-2-en-4-yl group.

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include an ethynyl group and a propargyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, and an o-hexadecanoylaminophenyl group. The phenyl group which may have a substituent is preferable.

  The heterocyclic group is a monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and they may be further condensed. These heterocyclic groups are preferably 5- or 6-membered heterocyclic groups, and the hetero atoms of the ring structure are preferably oxygen atoms, sulfur atoms and nitrogen atoms. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. The heterocyclic ring in the heterocyclic group includes pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, quinazoline ring, cinnoline ring, phthalazine ring, quinoxaline ring, pyrrole ring, indole ring, furan ring Benzofuran ring, thiophene ring, benzothiophene ring, pyrazole ring, imidazole ring, benzimidazole ring, triazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, isothiazole ring, benzisothiazole ring, thiadiazole ring, Examples include isoxazole ring, benzisoxazole ring, pyrrolidine ring, piperidine ring, piperazine ring, imidazolidine ring and thiazoline ring.

  The aliphatic oxy group (typically an alkoxy group) includes a substituted or unsubstituted aliphatic oxy group (typically an alkoxy group), and preferably has 1 to 30 carbon atoms. Examples include methoxy group, ethoxy group, isopropoxy group, n-octyloxy group, methoxyethoxy group, hydroxyethoxy group, and 3-carboxypropoxy group.

  The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group and the like. Preferably, it is a phenyloxy group that may have a substituent.

  The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. Examples of the acyloxy group include formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group and the like.

  The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. Examples of carbamoyloxy groups include N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octyl A carbamoyloxy group can be exemplified.

  The aliphatic oxycarbonyloxy group (typically an alkoxycarbonyloxy group) preferably has 2 to 30 carbon atoms and may have a substituent. Examples thereof include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group.

  The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, and a pn-hexadecyloxyphenoxycarbonyloxy group. Preferable is a phenoxycarbonyloxy group which may have a substituent.

  The amino group includes an amino group, an aliphatic amino group (typically an alkylamino group), an arylamino group, and a heterocyclic amino group. The amino group is preferably a substituted or unsubstituted aliphatic amino group having 1 to 30 carbon atoms (typically an alkylamino group) or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples of amino groups include, for example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, hydroxyethylamino group, carboxyethylamino group, sulfoethylamino group, 3,5-Dicarboxyanilino group, 4-quinolylamino group and the like can be mentioned.

  The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. Examples of the acylamino group include formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.

  The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. Examples of the aminocarbonylamino group include carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group and the like. The term “amino” in this group has the same meaning as “amino” in the aforementioned amino group.

  The aliphatic oxycarbonylamino group (typically an alkoxycarbonylamino group) preferably has 2 to 30 carbon atoms and may have a substituent. Examples thereof include a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, and an N-methyl-methoxycarbonylamino group.

  The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group, and the like. The phenyloxycarbonylamino group which may have a substituent is preferable.

  The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. Examples of the sulfamoylamino group include a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, and an Nn-octylaminosulfonylamino group.

  The aliphatic (typically alkyl) or arylsulfonylamino group is a substituted or unsubstituted aliphatic sulfonylamino group having 1 to 30 carbon atoms (typically an alkylsulfonylamino group), or substituted or unsubstituted having 6 to 30 carbon atoms. A substituted arylsulfonylamino group (preferably a phenylsulfonylamino group which may have a substituent) is preferable. Examples thereof include a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, and a p-methylphenylsulfonylamino group.

  The aliphatic thio group (typically an alkylthio group) is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. Examples of the alkylthio group include a methylthio group, an ethylthio group, and an n-hexadecylthio group.

  The arylthio group is preferably a substituted or unsubstituted arylthio group having 6 to 12 carbon atoms. Examples of the arylthio group include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

  The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. Examples of the sulfamoyl group include N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfa group. A moyl group, an N- (N′-phenylcarbamoyl) sulfamoyl) group, and the like.

  An aliphatic (typically alkyl) or arylsulfinyl group is a substituted or unsubstituted aliphatic sulfinyl group having 1 to 30 carbon atoms (typically an alkylsulfinyl group), or a substituted or unsubstituted aryl having 6 to 30 carbon atoms. A sulfinyl group (preferably a phenylsulfinyl group which may have a substituent) is preferable. Examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, and a p-methylphenylsulfinyl group.

  An aliphatic (typically alkyl) or arylsulfonyl group is a substituted or unsubstituted aliphatic sulfonyl group having 1 to 30 carbon atoms (typically an alkylsulfonyl group) or a substituted or unsubstituted aryl having 6 to 30 carbon atoms. A sulfonyl group (preferably a phenylsulfonyl group which may have a substituent) is preferable. For example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl group and the like can be mentioned.

  The acyl group is a formyl group, a substituted or unsubstituted aliphatic carbonyl group having 2 to 30 carbon atoms (typically an alkylcarbonyl group), a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms (preferably a substituent). A phenylcarbonyl group which may be present) or a heterocyclic carbonyl group bonded to the carbonyl group via a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms. Examples thereof include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl group and the like.

  The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl group and the like. A phenyloxycarbonyl group which may have a substituent is preferable.

  The aliphatic oxycarbonyl group (typically an alkoxycarbonyl group) preferably has 2 to 30 carbon atoms and may have a substituent. Examples thereof include methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl group and the like.

  The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl group and the like.

  Examples of the aryl or heterocyclic azo group include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo group, and the like.

  Examples of the imide group include an N-succinimide group and an N-phthalimide group.

  In addition to these, there can be mentioned hydroxyl groups, cyano groups, nitro groups, the aforementioned dissociable groups (for example, sulfo group, carboxyl group, phosphono group) and substituents having an ethylenically unsaturated group.

  Each of these groups may further have a substituent, and examples of such a substituent include the above-described substituents.

R ¹¹ and R ¹² are each independently a cyano group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, from the viewpoint of effectively achieving the effects of the present invention, and more A cyano group and a substituted or unsubstituted alkoxycarbonyl group are preferable, and a cyano group is most preferable.

R ¹³ is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryl, from the viewpoint of effectively achieving the effects of the present invention. An oxycarbonyl group, a substituted or unsubstituted carbamoyl group, and a heterocyclic group, more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, and most preferably a substituted or unsubstituted alkyl group It is a group.

R ¹⁴ is preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acylamino, from the viewpoint of effectively achieving the effects of the present invention. More preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, and a 2-thienyl group, and most preferably A substituted alkyl group and a substituted or unsubstituted phenyl group.

R ¹⁵ and R ¹⁶ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl, from the viewpoint of effectively achieving the effects of the present invention. More preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and most preferably a substituted or unsubstituted alkyl group.

  Regarding the preferred combination of substituents of the compound represented by the formula (1), a compound in which at least one of these substituents is the preferred group is preferred, and more various substituents are the preferred groups. Compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

  The compound represented by the general formula (1) has at least one compound represented by the general formula (2) or a repeating unit represented by the general formula (P) from the viewpoint of effectively achieving the effects of the present invention. Particularly preferred is a compound comprising a seed.

<Compound represented by formula (2)>
The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2).
The compound represented by the general formula (2) is characterized in that, like the specific azo dye compound represented by the general formula (1), the coupling component is aminothiazole and the diazo component is imidazole, And an azo dye compound having a dimerization structure linked via an N-position on an imidazole ring.
Among the compounds represented by the general formula (1), the compound represented by the general formula (2) has particularly high solubility, heat resistance and light resistance to organic solvents, stability over time, and solvent resistance after curing. A colored curable composition having excellent properties can be obtained.

In the general formula (2), R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁶ , R ³¹ , R ³² , R ³⁴ , R ³⁵ , and R ³⁶ are each independently a hydrogen atom or a monovalent substituent. L ¹ represents a divalent linking group. R ²¹ and R ²² , R ²⁵ and R ²⁶ , R ³¹ and R ³² , and R ³⁵ and R ³⁶ may be bonded to each other to form a ring.

In the general formula (2), R ²¹ , R ²² , R ²⁴ , R ³¹ , R ³² , and R ³⁴ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent in R ²¹ , R ²² , R ²⁴ , R ³¹ , R ³² , and R ³⁴ include a halogen atom and an alkyl group having 1 to 30 carbon atoms (in this application, a cycloalkyl group and a bicycloalkyl group). , An alkenyl group having 2 to 30 carbon atoms (in the present application, an unsaturated aliphatic group having a double bond including a cycloalkenyl group and a bicycloalkenyl group), 2 carbon atoms -30 alkynyl group, aryl group having 6-30 carbon atoms, heterocyclic group having 3-30 carbon atoms, cyano group, aliphatic oxy group having 1-30 carbon atoms, aryloxy group having 6-30 carbon atoms, carbon C2-C30 acyloxy group, C1-C30 carbamoyloxy group, C2-C30 aliphatic oxycarbonyloxy group, C7-C30 aryloxycarbonyl Xoxy group, C0-30 amino group (including alkylamino group, anilino group and heterocyclic amino group), C2-30 acylamino group, C1-30 aminocarbonylamino group, C2 ˜30 aliphatic oxycarbonylamino group, C 7-30 aryloxycarbonylamino group, C 0-30 sulfamoylamino group, C 1-30 alkyl or arylsulfonylamino group, C 1 -30 alkylthio group, C0-30 sulfamoyl group, C1-30 alkyl or arylsulfinyl group, C1-30 alkyl or arylsulfonyl group, C2-30 acyl group, carbon number 7-30 aryloxycarbonyl group, C2-C30 aliphatic oxycarbonyl group, C1-C3 Examples thereof include a carbamoyl group of 0, an aryl or heterocyclic azo group having 3 to 30 carbon atoms, and an imide group, and each group may further have a substituent.

In the general formula (2), R ²⁵ , R ²⁶ , R ³⁵ , and R ³⁶ each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent in R ²⁵ , R ²⁶ , R ³⁵ , and R ³⁶ include an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, and carbon. An aryl group having 6 to 30 carbon atoms, a heterocyclic group having 3 to 30 carbon atoms, an acyl group having 2 to 30 carbon atoms, an aryloxycarbonyl group having 7 to 30 carbon atoms, an aliphatic oxycarbonyl group having 2 to 30 carbon atoms, Examples thereof include carbamoyl groups having 1 to 30 carbon atoms, and each group may further have a substituent.

In the general formula (2), L ¹ represents a divalent linking group. Examples of the divalent linking group represented here include alkylene groups having 2 to 30 carbon atoms (eg, ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene), and those having 2 to 30 carbon atoms. Alkenylene group (eg, ethenylene, propenylene), C2-C30 alkynylene group (eg, ethynylene, 1,3-propynylene), C6-C30 arylylene group (eg: phenylene or naphthylene), C3-30 A divalent heterocyclic group (eg, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group), -O -, - CO -, - NR- (R is an alkyl or aryl group of which a hydrogen atom or a _{C1-30), - S -, - SO} 2 -, - SO- or total number of carbon atoms which can be a combination thereof 0 ~ 30 Valent substituent (eg: o-xylylene, m- xylylene, p- xylylene), and the like, each group may further have a substituent.

R ²¹ , R ²² , R ³¹ , and R ³² are each independently preferably a cyano group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryl, from the viewpoint of effectively achieving the effects of the present invention. An oxycarbonyl group, more preferably a cyano group, a substituted or unsubstituted alkoxycarbonyl group, and most preferably a cyano group.

R ²⁴ and R ³⁴ are each independently preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, from the viewpoint of effectively achieving the effects of the present invention. A substituted or unsubstituted acylamino group, more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, and a 2-thienyl group. And most preferably an unsubstituted alkyl group or a substituted or unsubstituted phenyl group.

R ²⁵ , R ²⁶ , R ³⁵ , and R ³⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, from the viewpoint of effectively achieving the effects of the present invention. A substituted or unsubstituted acyl group, more preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and most preferably a substituted or unsubstituted alkyl group.

L ¹ is preferably a substituted or unsubstituted alkylene having 2 to 8 carbon atoms or xylylene, more preferably a substituted or unsubstituted carbon having 3 to 6 carbon atoms, from the viewpoint of effectively achieving the effects of the present invention. Alkylene, o-xylylene and m-xylylene, most preferably unsubstituted alkylene having 3 to 4 carbon atoms or o-xylylene.

  As for the preferred combination of substituents of the compound represented by the general formula (2), a compound in which at least one of these substituents is the preferred group is preferred, and more various substituents are the preferred groups. Certain compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

From the viewpoint of effectively achieving the effects of the present invention, R ²¹ is preferably a cyano group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, and R ²² is a cyano group, substituted Or an unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, and R ²⁴ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted or unsubstituted An unsubstituted acylamino group, R ²⁵ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, and R ²⁶ is a hydrogen atom, substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, R ³¹ is a cyano group, a substituted or unsubstituted a Job aryloxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, R ³² is a cyano group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, R ³⁴ is a substituted or unsubstituted A substituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acylamino group, and R ³⁵ is a hydrogen atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted An aryl group, a substituted or unsubstituted acyl group, R ³⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group, and L is substituted or unsubstituted A combination which is unsubstituted alkylene having 2 to 8 carbon atoms or xylylene.

From the viewpoint of effectively achieving the effect of the present invention, more preferably, R ²¹ is a cyano group, a substituted or unsubstituted alkoxycarbonyl group, and R ²² is a cyano group, a substituted or unsubstituted alkoxycarbonyl group. R ²⁴ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, or a 2-thienyl group, and R ²⁵ is a substituted or unsubstituted group. An alkyl group, a substituted or unsubstituted aryl group, R ²⁶ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and R ³¹ is a cyano group, a substituted or unsubstituted alkoxycarbonyl group , R ³² is a cyano group, a substituted or unsubstituted alkoxycarbonyl group, R ³⁴ is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl , 2-pyridyl, 3-pyridyl, 4-pyridyl group, a 2-thienyl ^{group, R 35} is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl ^{group, R 36} is a substituted or unsubstituted A combination is a substituted alkyl group, a substituted or unsubstituted aryl group, and L is a substituted or unsubstituted alkylene having 3 to 6 carbon atoms, o-xylylene, or m-xylylene.

Most preferably, R ²¹ is a cyano group, R ²² is a cyano group, and R ²⁴ is an unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or An unsubstituted phenyl group, R ²⁵ is a substituted or unsubstituted alkyl group, R ²⁶ is a substituted or unsubstituted alkyl group, R ³¹ is a cyano group, and R ³² is a cyano group, R ³⁴ is an unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted phenyl group, R ³⁵ is a substituted or unsubstituted alkyl group, and R ³⁶ is a substituted or unsubstituted alkyl group. , L is an unsubstituted alkylene group having 3 to 4 carbon atoms and o-xylylene.

<Compound containing at least one repeating unit represented by formula (P)>
In the compound represented by the general formula (1), a group derived from a polymer compound may be bonded as a substituent represented by R ^{11 to} R ¹⁶ in the general formula (1). It is also a preferred embodiment that it is an azo dye polymer compound characterized in that it is a compound containing at least one repeating unit represented by
As for the compound containing at least one repeating unit represented by the general formula (P), the coupling component is aminothiazole and the diazo component is imidazole, similarly to the compound represented by the general formula (1). And an azo dye polymer compound characterized by being a polymer compound having at least one repeating unit having a residue obtained by removing one hydrogen atom from the dye in the side chain.
Among the specific azo dye compounds, a compound represented by an azo dye polymer compound containing at least one repeating unit represented by the following general formula (P) has particularly high solubility, heat resistance, and light resistance in an organic solvent. A colored curable composition having excellent stability over time and solvent resistance after curing can be obtained.

In general formula (P), R ^P1 , R ^P2 and R ^P3 each independently represent a hydrogen atom or a monovalent substituent, and * represents a residue obtained by removing one hydrogen atom from general formula (1). And n represents an integer of 1 to 100.

In the general formula (P), R ^P1 , R ^P2 and R ^P3 each independently represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent in R ^P1 , R ^P2 , and R ^P3 include a halogen atom and an alkyl group having 1 to 30 carbon atoms (in this specification, a saturated aliphatic group including a cycloalkyl group and a bicycloalkyl group). ), An alkenyl group having 2 to 30 carbon atoms (in the present specification, an unsaturated aliphatic group having a double bond including a cycloalkenyl group and a bicycloalkenyl group), and an alkenyl group having 2 to 30 carbon atoms. Alkynyl group, C6-C30 aryl group, C3-C30 heterocyclic group, cyano group, C1-C30 aliphatic oxy group, C6-C30 aryloxy group, C2-C2 30 acyloxy groups, carbamoyloxy groups having 1 to 30 carbon atoms, aliphatic oxycarbonyloxy groups having 2 to 30 carbon atoms, aryloxycarbonyloxy groups having 7 to 30 carbon atoms, carbon numbers -30 amino groups (in this specification, including alkylamino groups, anilino groups and heterocyclic amino groups), acylamino groups having 2 to 30 carbon atoms, aminocarbonylamino groups having 1 to 30 carbon atoms, 2 carbon atoms ˜30 aliphatic oxycarbonylamino group, C 7-30 aryloxycarbonylamino group, C 0-30 sulfamoylamino group, C 1-30 alkyl or arylsulfonylamino group, C 1 -30 alkylthio group, C0-30 sulfamoyl group, C1-30 alkyl or arylsulfinyl group, C1-30 alkyl or arylsulfonyl group, C2-30 acyl group, carbon number 7-30 aryloxycarbonyl group, C2-C30 aliphatic oxycarbonyl group, C1-C3 Examples thereof include a carbamoyl group of 0, an aryl or heterocyclic azo group having 3 to 30 carbon atoms, and an imide group, and each group may further have a substituent.

In general formula (P), n represents the integer of 1-100.
In the general formula (P), * represents a bond that binds to a residue obtained by removing one hydrogen atom from the general formula (1).

R ^P1 , R ^P2 and R ^P3 are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, substituted or substituted, from the viewpoint that the effects of the present invention can be effectively achieved. An unsubstituted acyl group, more preferably a hydrogen atom or an unsubstituted alkyl group, and most preferably a hydrogen or methyl group.

  n is preferably 1 to 75, more preferably 2 to 50, and most preferably 2 to 25, from the viewpoint of effectively achieving the effects of the present invention.

The residue is preferably the same as the preferred substituent of the general formula (1) from the viewpoint of effectively producing an effect. The site for removing one hydrogen atom is preferably a hydrogen atom of a substituent of R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ , more preferably a hydrogen atom of a substituent of R ¹³ , R ¹⁵ , and R ¹⁶ And most preferably a hydrogen atom of the substituent of R ¹³ .

  A preferred embodiment of the compound containing at least one repeating unit represented by the general formula (P) is a copolymer polymer dye compound having a repeating unit represented by the general formula (P) and a repeating unit having an acidic group. It is.

Examples of the monomer of the copolymer component used as the repeating unit having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2- (meth) acrylamide-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include mono (2- (meth) acryloyloxy phosphate). Ethyl ester), phosphoric acid mono (1-methyl-2- (meth) acryloyloxyethyl ester), and the like.

  The compound containing at least one repeating unit represented by formula (P) in the present invention preferably contains a repeating unit derived from a monomer having an acidic group as described above. By including such a repeating unit, when the pigment dispersion composition of the present invention is applied to a colored photosensitive composition, the development removability of an unexposed portion is excellent.

The compound containing at least one repeating unit represented by formula (P) in the present invention may contain only one type of repeating unit derived from a monomer having an acidic group, or may contain two or more types. May be included.
In the compound containing at least one repeating unit represented by the general formula (P), the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more, particularly preferably 50 mgKOH / g to 200 mg KOH / g. That is, in terms of suppressing the formation of precipitates in the developer, the content of the repeating unit derived from the monomer having an acidic group is preferably 50 mgKOH / g or more. Furthermore, in order to effectively suppress the formation of secondary aggregates, which are aggregates of primary particles of the pigment, or to effectively weaken the cohesive force of the secondary aggregates, it is derived from a monomer having an acidic group. The content of the repeating unit is preferably 50 mgKOH / g to 200 mgKOH / g.

  The compound containing at least one repeating unit represented by the general formula (P) may further contain a repeating unit derived from a vinyl monomer having another structure that can be copolymerized, as long as the effect is not impaired. Good.

  Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds. In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.
Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

The compound containing at least one repeating unit represented by the general formula (P) in the present invention includes the repeating unit represented by the general formula (P) in the molecule and the repeating unit represented by the general formula (P). It is preferable to contain 20 mass%-99.5 mass% in the total mass of the compound which contains at least 1 sort, More preferably, it is 40 mass%-95 mass%.
Within this range, the spectral properties and alkali developability of the thin film are good.

The preferred molecular weight of the compound containing at least one repeating unit represented by formula (P) in the present invention is in the range of 5000 to 100,000 in terms of weight average molecular weight (Mw), and in the range of 2500 to 50000 in terms of number average molecular weight (Mn). It is preferable that More preferably, the weight average molecular weight (Mw) is in the range of 10,000 to 50,000, and the number average molecular weight (Mn) is in the range of 5,000 to 30,000.
In particular, the weight average molecular weight (Mw) is most preferably in the range of 10,000 to 30000, and the number average molecular weight (Mn) is in the range of 5000 to 15000. From the viewpoint of developability when producing a color filter with a colored curable composition, the weight average molecular weight (Mw) is preferably 30000 or less.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited thereto. The following exemplified compounds (71) to (118) are also exemplified compounds of the general formula (2).
In addition, the exemplary compounds (P1) to (P50) are exemplary compounds of a compound including at least one repeating unit represented by the general formula (P), and these exemplary compounds are also represented by the general formula (1). This is a specific example of the compound.

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , and R ⁴⁶ of the following exemplary compounds (1) to (70) and (119) to (126) are each represented by the following formula (3) It is a group.

R ⁵¹ , R ⁵² , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , and L ¹ in the following exemplified compounds (71) to (114) are groups represented by the following formula (4).

A and B of the exemplary compounds (P1) to (P100) shown below are repeating units (A-1) to (A-20) and (B-1) to (B to 27) having the structures shown below, respectively. is there.
The number average molecular weight (Mn) of the following exemplary compounds (P1) to (P100) is in the range of 5,000 to 25,000, and the weight average molecular weight (Mw) is in the range of 6,000 to 30,000. The molecular weight distribution index (Mw / Mn) is in the range of 1.30 to 2.50.

These azo dye compounds can be easily synthesized according to the method described in US Pat. No. 5,789,560. That is, the method for synthesizing the azo dye compound represented by the general formula (1) or (2) in the present invention is to perform synthesis by diazo coupling generally performed and then alkylation using an alkylating agent. Can do.
Specifically, the amino group of the 2-aminoimidazole derivative represented by the general formula (A) is converted to a diazonium salt of the general formula (B) with a diazotizing agent, and the diazonium salt and the general formula (C) The compound represented by the general formula (D) is obtained by a coupling reaction with the represented 2-aminothiazole derivative. Then, it can synthesize | combine easily by alkylating general formula (D) by general formula (E) etc. on basic conditions. Specific examples are given in the examples.
The compound containing at least one repeating unit represented by the general formula (P) can be synthesized by polymerizing the azo dye compound represented by the general formula (1) by an ordinary method.

In general formula (A), R ¹ and R ² each independently represent a hydrogen atom or a monovalent substituent. R ¹ and R ² may be bonded to each other to form a ring.

In the general formula (B), ^{R 1,} and ^{R 2, R 1,} and ^{R 2} as synonymous in the general formula (A). X ⁻ is a counter anion of the diazonium salt.

In general formula (C), R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent substituent.

In the general formula ^{(D), R 1, R} 2, R 4, R 5, and ^{R 1, R 2, R 4} , R 5, and ^{R 6} as defined in ^{R 6} has the general formula (A) ~ (C) It is.

In general formula (E), R ³ represents a monovalent substituent, and Y represents a leaving group (for example, a halogen atom, a tosyl group, etc.).

Many of the compounds represented by the general formula (A) are commercially available (for example, catalog number A1292 manufactured by Tokyo Chemical Industry Co., Ltd.). The compound represented by the general formula (C) can be synthesized by a conventionally known method (for example, J. Chem. Soc. Perkin Tr).
ans. 1 (1984) 2 pp. 147-153). Many of the compounds represented by the general formula (E) are commercially available (for example, catalog number B0411 manufactured by Tokyo Chemical Industry Co., Ltd.).

  The total concentration of the specific azo dye compound represented by the general formula (1) in the colored curable composition varies depending on the molecular weight and the molar extinction coefficient, but is 0.5 to 80% by mass is preferable, 0.5 to 70% by mass is more preferable, and 1 to 70% by mass is particularly preferable.

In the colored curable composition of the present invention, a specific azo dye compound and a dye having another structure may be used in combination. There is no restriction | limiting in particular as a pigment | dye of another structure, The well-known pigment | dye conventionally used as a color filter use can be used. For example, JP 2002-14220, JP 2002-14221, JP 2002-14222, JP 2002-14223, US Pat. No. 5,667,920, US Pat. , 059,500 specification, and the like.
The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

<Colored curable composition>
Next, the colored curable composition of the present invention will be described.
The colored curable composition of the present invention contains at least one specific azo dye compound described above and a polymerizable compound. The polymerizable compound is polymerized or cross-linked by exposure to UV light of 400 nm or less or heat, and the colored curable composition is insolubilized in an alkali developer, so that the exposed portion and the unexposed portion are distinguished in the photolithography method. Patterning can be performed.
In the ink jet method, cured colored pixels can be obtained.

In order to further increase the speed of the curing reaction, the colored curable composition preferably contains a polymerization initiator that generates radicals and acids, which is essential when pixels are formed by the photolithography method. When forming a pixel by the inkjet method, the polymerization initiator is not essential because it can be cured by heat, but it is preferably used for a colored curable composition.
Furthermore, a binder, a surfactant, and other additives can be used for the colored curable composition.

<Polymerizable compound>
As the polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group is preferable, and a compound having three or more is more preferable. Examples thereof include compounds described in paragraphs [0254] to [0257] of JP-A-2008-292970, paragraphs [0054] to [0068] of JP-A-2009-13206, and (meth) acrylic. It is preferable to contain at least one selected from a system monomer, an epoxy monomer, and an oxetanyl monomer.

  In particular, an acrylic compound having three or more acryloyl groups in the molecule is preferable. For example, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) (Meth) acrylate after adding ethylene oxide, propylene oxide, caprolactone to polyfunctional alcohol such as acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylolethane And those obtained by poly (meth) acrylate conversion of pentaerythritol or dipentaerythritol.

The content of the polymerizable compound in the colored curable composition is preferably 0.1% by mass to 90% by mass, and more preferably 1.0% by mass to 80% by mass with respect to the solid content in the colored curable composition. Preferably, 2.0 mass%-70 mass% is especially preferable.
In particular, when used as an inkjet ink, 30 to 80% by mass in the solid content of the colored curable composition is preferable, and 40 to 80% by mass is more preferable. When the amount of the polymerizable compound used is within the above range, the pixel portion is sufficiently polymerized, and therefore, scratches due to insufficient film strength of the pixel portion are less likely to occur. Furthermore, when the transparent conductive film is applied, it is difficult to generate cracks or reticulation, the solvent resistance when providing the alignment film is improved, and the voltage holding ratio is not lowered.
Here, the solid content of the colored curable composition for specifying the blending ratio includes all components except the solvent, and a liquid polymerizable compound is also included in the solid content.
Hereinafter, the colored curable composition used in the photolithography method will be described.

<Photopolymerization initiator>
The colored curable composition of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable compound, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
Examples of the photopolymerization initiator include compounds described in paragraphs [0260] to [0271] of JP-A-2008-292970.

  The content of the photopolymerization initiator in the colored curable composition is preferably 0.01 to 50 mass%, more preferably 1 to 30 mass%, and more preferably 1 to 20 mass% with respect to the solid content of the polymerizable compound. Is particularly preferred. When the content is within the above range, the polymerization proceeds well and good film strength can be obtained.

<Binder>
The colored curable composition preferably contains a binder other than the compound containing at least one repeating unit represented by the general formula (P). The binder is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
The 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 the polymers described in paragraphs [0227] to [0234] of JP-A No. 2008-292970.
The content of the binder in the colored curable composition is preferably 0.1% by mass to 50% by mass, more preferably 0.1% by mass to 40% by mass with respect to the solid content in the colored curable composition. 0.1% by mass to 30% by mass is particularly preferable.

<Crosslinking agent>
It is also preferable to add a crosslinking agent to 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, paragraph [0237] of JP-A-2008-292970 To [0253].
When it contains a crosslinking agent, it is preferably 1 to 70% by mass, more preferably 5 to 50% by mass, and particularly preferably 7 to 30% by mass with respect to the total solid content (mass) of the colored curable composition. When the content is within the above range, it is possible to maintain a sufficient degree of curing and elution of unexposed areas. If the crosslinking agent is insufficient, the degree of cure of the exposed area may be insufficient, and if the crosslinking agent is excessive, the elution property of the unexposed area may be significantly reduced.

<Solvent>
When preparing the colored curable composition of this invention, a solvent can generally be contained. The solvent used is not particularly limited as long as it satisfies the solubility of each component of the composition and the applicability of the colored curable composition, but in particular, considers the solubility, applicability, and safety of the binder. Is preferably selected.
Examples of the solvent include those described in paragraph [0272] of JP-A-2008-292970.
Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol Acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

<Various additives>
In the colored curable composition of the present invention, various additives as necessary, for example, fillers, polymer compounds other than the above, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. Can be blended. Examples thereof include the additives described in paragraphs [0274] to [0276] of JP-A-2008-292970.

<Preparation method of colored curable composition>
In preparing the colored curable composition of the present invention, the above-described components of the composition may be combined at once, or may be sequentially added after each component is dissolved in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. A composition may be prepared by dissolving all the components in a solvent at the same time. If necessary, each component is appropriately made into two or more solutions, and these solutions are mixed at the time of use (at the time of application). And may be prepared as a composition.
The composition prepared as described above is preferably filtered after using a filter having a pore size of 0.01 to 3.0 μm, more preferably a pore size of about 0.05 to 0.5 μm, and then used. You can also.

The colored curable composition of the present invention can be suitably used for forming colored pixels such as color filters used in liquid crystal display devices (LCDs) and solid-state imaging devices (for example, CCDs, CMOSs, etc.). In particular, it can be suitably used for forming color filters for solid-state imaging devices such as CCDs and CMOSs.
The colored curable composition of the present invention is particularly suitable for forming a color filter for a solid-state imaging device in which a colored pattern is formed in a thin film with a very small size and a good rectangular cross-sectional profile is required.

Specifically, when the pixel pattern size (side length of the pixel pattern viewed from the substrate normal direction) constituting the color filter is 2 μm or less (for example, 0.5 to 2.0 μm), the amount of colorant increases. As a result, the line width sensitivity is deteriorated and the DOF margin is narrowed. As a result, the pattern formability is easily impaired. This is particularly noticeable when the pixel pattern size is 1.0 to 1.7 μm (further 1.2 to 1.5 μm). In addition, in the case of a thin film having a thickness of 1 μm or less, the amount of components that contribute to photolithographic properties excluding the colorant in the film is relatively reduced, and the amount of other components is further reduced by the increase in the amount of colorant. Sensitivity is increased and the pattern is easily peeled off in the low exposure area. In this case, heat sagging is likely to occur when heat treatment such as post-baking is performed. These are particularly remarkable when the film thickness is 0.005 μm to 0.9 μm (further 0.1 μm to 0.7 μm).
On the other hand, when the colored curable composition of the present invention is used, a color filter having a good cross-sectional profile can be produced with excellent pattern formation even with the pixel pattern size of 2 μm or less as described above.

<Pattern formation method using colored curable composition>
A method for forming a color filter by a photolithography method using the colored curable composition described in the present specification includes a step of applying a colored layer on a support and forming a colored layer through a mask. And a step of forming a pattern by development after the exposure. For example, the method described in [0277] to [0284] of JP-A-2008-292970 can be mentioned in detail. It is done.

-Post-curing process-
In the present invention, it is preferable to carry out a post-curing step of further curing the pattern after the step of forming a pattern by the above-described development.
The post-curing step is carried out by heating and / or exposure (ultraviolet irradiation), but the pattern obtained is further cured to dissolve the pattern in the step of forming a colored layer for forming the next color pattern. It can prevent or improve the solvent resistance of the pixel of the obtained color filter.
The post-curing step is preferably performed by ultraviolet irradiation.

-Post curing process UV irradiation-
In the ultraviolet irradiation process used for curing the pattern by post-exposure, an irradiation light amount 10 times or more of the exposure amount [mJ / cm ² ] in the exposure process before development is applied to the pattern after the development process in the pattern formation process [ mJ / cm ² ] of ultraviolet light (UV light). By irradiating the developed pattern with UV light for a predetermined time between the development processing in the pattern forming step and the heat treatment described later, it is possible to effectively prevent color migration when heated later. If the amount of irradiation light in this step is less than 10 times, color transfer between colored pixels and between upper and lower layers cannot be prevented.
Especially, the irradiation light quantity of UV light is preferably 12 times or more and 200 times or less, more preferably 15 times or more and 100 times or less the exposure amount at the time of exposure in the pattern forming step.

  The post-exposure can be performed with g-line, h-line, i-line, KrF, ArF, UV light, electron beam, X-ray, etc., but g-line, h-line, i-line, UV light is preferable, and UV is particularly preferable. Light is preferred. When performing irradiation with UV light (UV cure), it is preferable to carry out at a low temperature of 20 ° C. or more and 50 ° C. or less (preferably 25 ° C. or more and 40 ° C. or less). The wavelength of the UV light preferably includes a wavelength in the range of 200 to 300 nm. As the light source, for example, a high pressure mercury lamp, a low pressure mercury lamp, or the like can be used. The irradiation time is 10 to 180 seconds, preferably 20 to 120 seconds, and more preferably 30 to 60 seconds.

As a light source for irradiating UV light, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a DEEP UV lamp, or the like can be used. Among them, the irradiated ultraviolet light includes light having a wavelength of 275 nm or less, and the irradiation illuminance [mW / cm ² ] of the light having a wavelength of 275 nm or less is 5% or more with respect to the integrated irradiation illuminance of all the wavelength light in the ultraviolet light. The thing which can irradiate the light which is is preferable. By setting the irradiation illuminance of light having a wavelength of 275 nm or less in ultraviolet light to 5% or more, the effect of suppressing color transfer between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively enhanced. From this point, it is preferable to use a light source different from a light source such as an i-line or the like used for exposure in the pattern forming step, specifically, a high pressure mercury lamp, a low pressure mercury lamp, or the like. Among these, for the same reason as described above, 7% or more is preferable with respect to the integrated irradiation illuminance of all wavelength light in ultraviolet light. Moreover, the upper limit of the irradiation illuminance of light having a wavelength of 275 nm or less is preferably 25% or less.

The integrated irradiation illuminance is a curve with the illuminance for each spectral wavelength (radiant energy passing through a unit area per unit time; [mW / m ² ]) as the vertical axis and the wavelength [nm] of light as the horizontal axis. When drawn, it means the sum (area) of the illuminance of each wavelength light included in the irradiation light.

It is preferable that the integrated irradiation illuminance in the ultraviolet light irradiated in the post-exposure ultraviolet irradiation step is 200 mW / cm ² or more. When the integrated irradiation illuminance is 200 mW / cm ² or more, the effect of suppressing color transfer between colored pixels and the upper and lower layers and the effect of improving light resistance can be more effectively enhanced. Among them, preferred is ^{250~2000mW / cm 2, 300~1000mW / cm} 2 is more preferable.
Moreover, it is preferable to implement post-heating at 100 to 300 degreeC using a hotplate or oven, More preferably, it is 150 to 250 degreeC. The post-heating time is preferably 30 seconds to 30000 seconds, and more preferably 60 seconds to 1000 seconds.

  In the post-curing step, post-exposure and post-heating may be used together. In this case, either may be performed first, but it is preferable to perform post-exposure prior to post-heating. This is because curing is promoted by post-exposure, thereby suppressing deformation of the shape due to heat sagging and soaking of the pattern seen in the post-heating process.

  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 pattern forming step (and the curing step if necessary) is repeated in accordance with the desired number of colors to obtain a color filter configured in a desired number of hues. Can be produced.

Next, the colored curable composition preferably used in the inkjet method will be described.
The structure of the colored curable composition when used as an inkjet ink is as described above, and particularly preferred embodiments are shown below.
When the curable coloring composition of the present invention is used as an inkjet ink, the ink storage stability is excellent, and aggregation and decomposition of the ink are suppressed. Also, during continuous and intermittent discharge, it is difficult for discharge disturbance such as flying bend and non-discharge, excellent discharge stability, recovery after a certain period of rest, non-discharge etc. Excellent recoverability.

In the colored curable composition used for the inkjet ink, the azo dye compound represented by the general formula (1) has a total content in the inkjet ink of 1 to 20% by mass with respect to the total amount of the ink. Preferably, 5 to 15% by mass is more preferable. When the amount is less than 1% by mass, the film thickness may be increased in order to achieve an optical density necessary for the color filter. Therefore, it is necessary to increase the thickness of the black matrix as a partition wall, which is not preferable because it is difficult to form the black matrix. When it exceeds 20% by mass, the ink viscosity becomes high and it becomes difficult to discharge, and it may be difficult to dissolve in a solvent.

<Solvent>
The colored curable composition as the ink-jet ink of the present invention contains a solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component and the boiling point of the solvent described later, but is preferably selected in consideration of the solubility, coating property, and safety of the binder described later. Specific examples of the solvent include the solvents described in paragraphs [0030] to [0040] of JP-A-2009-13206.

  The content of the solvent in the inkjet ink of the present invention is preferably from 30 to 90% by mass, more preferably from 50 to 90% by mass, based on the total amount of the ink. When the amount is 30% by mass or more, the amount of ink ejected in one pixel is maintained, and the wetting and spreading of the ink in the pixel is good. Further, when it is 90% by mass or less, the amount of components other than the solvent for forming a functional film (for example, a pixel or the like) in the ink can be kept at a predetermined amount or more. As a result, when forming a color filter, the required amount of ink per pixel does not increase too much. For example, when ink is applied to the concave portion partitioned by the partition wall by the ink jet method, the ink overflows from the concave portion. And the occurrence of color mixing with adjacent pixels can be suppressed.

  The ink-jet ink of the present invention preferably contains a solvent having a high boiling point among the above-mentioned solvents from the viewpoints of ink discharge performance with respect to the nozzle and wettability with respect to the substrate. Since the solvent having a low boiling point evaporates quickly even on the ink jet head, it easily causes an increase in the viscosity of the ink on the head, precipitation of solids, and the like, and is often accompanied by a deterioration in dischargeability. Also, when the ink lands on the substrate surface and spreads on the substrate surface, the viscosity of the ink increases due to the evaporation of the solvent at the edge of the wet spread, and the phenomenon of pinning (PINING) causes the wetting and spreading. It may be suppressed.

The boiling point of the solvent used in the present invention is preferably 130 to 280 ° C. If it is lower than 130 ° C., it may not be preferable in terms of the uniformity of the shape of pixels in the surface. If it is higher than 280 ° C., it may not be preferable in terms of solvent removal by pre-baking. The boiling point of the solvent means a boiling point under a pressure of 1 atm, and a compound dictionary (Chapman & Hall)
It can be known from the physical property value table. These may be used alone or in combination of two or more.

  In addition, when the ink-jet ink described above does not contain a polymerizable monomer, which will be described later, the thickness of the remaining ink (color pixel) obtained by removing the solvent contained in the ink is reduced, so that the substrate is used for the purpose of preventing color mixing. The height of the partition formed on the top can be reduced, which is preferable from the viewpoint of cost and productivity.

<Binder>
The ink-jet ink of the present invention may contain a binder for the purpose of adjusting the viscosity and adjusting the ink hardness. As the binder, a binder resin that is simply dried and solidified such that it is composed only of a resin that is not polymerized by itself may be used. However, in order to impart sufficient strength, durability, and adhesion to the coating film, a binder that can cure the pixel by a polymerization reaction after forming a pixel pattern on the substrate by an inkjet method is used. For example, a binder that can be polymerized and cured, such as a photocurable binder that can be polymerized and cured by visible light, ultraviolet light, electron beam, or the like, or a thermosetting binder that can be polymerized and cured by heating. Can be used.

<Crosslinking agent>
The epoxy monomer (epoxy group-containing monomer) and the thermosetting binder resin can usually be combined with a crosslinking agent. As the cross-linking agent, the curing agent and the accelerator described in Chapter 3 of “Review Epoxy Basic Fundamentals I” issued on November 19, 2003, published by the Epoxy Resin Technology Association, can be suitably used. Carboxylic anhydride or polyvalent carboxylic acid can be used.

<Surfactant>
A surfactant may be further used in the inkjet ink of the present invention. As examples of the surfactant, those disclosed in JP-A-7-216276, paragraph [0021], JP-A-2003-337424, and JP-A-11-133600 are preferable. As mentioned. As for content of surfactant, 5 mass% or less is preferable with respect to coloring composition whole quantity.

Examples of other additives include other additives described in paragraphs [0058] to [0071] of JP-A No. 2000-310706.
In the inkjet ink composition, the content of the solvent is preferably 30 to 90% by mass, and more preferably 50 to 85% by mass with respect to the total amount of the colored curable composition. As for content of surfactant, 0.1-5 mass% is preferable with respect to coloring composition whole quantity.

<Inkjet ink manufacturing method>
For the production of the inkjet ink of the present invention, a known inkjet ink production method can be applied. For example, after dissolving the compound represented by the general formula (1) in a solvent, each component (for example, a polymerizable compound and a binder) necessary for the inkjet ink can be dissolved to prepare the inkjet ink. .

  When preparing a solution of the polymerizable compound, if the solubility of the material used in the solvent is low, treatment such as heating or ultrasonic treatment is performed within a range in which the polymerizable compound does not cause a polymerization reaction. It can be performed as appropriate.

  In the case where the compound represented by the general formula (1) is dispersed in an aqueous medium, JP-A Nos. 11-286637, 2001-240763 (Japanese Patent Application No. 2000-78491), and JP-A No. 2001-262039 (Japanese Patent Application No. 2000-). 80259) and JP-A No. 2001-247788 (Japanese Patent Application No. 2000-62370), fine particles containing a compound represented by the general formula and an oil-soluble polymer are dispersed in an aqueous medium, or JP-A No. 2001-262018. (Japanese Patent Application No. 2000-78454), Japanese Patent Application Laid-Open No. 2001-240763 (Japanese Patent Application No. 2000-78491), and Japanese Patent Application Laid-Open No. 2001-335734 (Japanese Patent Application No. 2000-203856). The represented compound may be dispersed in an aqueous medium. The specific method for dispersing the compound represented by the general formula (1) in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are described in the above-mentioned patent documents. A thing can be preferably used. Or you may disperse | distribute the compound represented by each general formula to a fine particle state with solid. At the time of dispersion, a dispersant or a surfactant can be used.

  Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patent documents, JP-A-5-148436, 5-295212, 7-97541, 7-82515, 7-185858, Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application Laid-Open No. 2001-271003 (Japanese Patent Application No. 2000-87539), and can also be used for preparing the ink-jet ink of the present invention.

<Physical properties of ink-jet ink>
The physical property value of the inkjet ink of the present invention is not particularly limited as long as it can be ejected by the inkjet head, but the viscosity at the time of ejection is preferably 2 to 30 mPa · s from the viewpoint of stable ejection. 20 mPa · s is more preferable. Moreover, when ejecting with an apparatus, it is preferable to maintain the temperature of the inkjet ink at a substantially constant temperature in the range of 20 to 80 ° C. If the temperature of the device is set to a high temperature, the viscosity of the ink decreases and it becomes possible to eject higher viscosity ink. However, due to the increase in temperature, the ink is denatured by heat and the thermal polymerization reaction occurs in the head. The temperature of the apparatus is preferably in the range of 20 to 80 ° C. because the solvent evaporates on the surface of the nozzle that ejects ink or nozzle clogging easily occurs.

  The viscosity is measured by using a commonly used E-type viscometer (for example, an E-type viscometer (RE-80L) manufactured by Toki Sangyo Co., Ltd.) with the inkjet ink held at 25 ° C. Value.

  Further, the surface tension (static surface tension) at 25 ° C. of the inkjet ink is preferably 20 to 40 mN / m, preferably 20 to 35 mN / m in terms of improving wettability with respect to a non-permeable substrate and discharge stability. m is more preferable. Moreover, when discharging with an apparatus, it is preferable to maintain the temperature of the ink for inkjet in the range of 20-80 degreeC, and it is preferable to make the surface tension at that time into 20-40 mN / m. In order to keep the temperature of the inkjet ink constant with a predetermined accuracy, the ink temperature detection means, the ink heating or cooling means, and the control means for controlling the heating or cooling according to the detected ink temperature are provided. Preferably it is. Alternatively, it is also preferable to have a means for reducing the influence on the ink physical property change by controlling the energy applied to the means for ejecting ink according to the ink temperature.

  The above-described surface tension is measured by a Wilhelmy method using a commonly used surface tension meter (for example, surface tension meter FACE SURFACE TENSIOMETER CBVB-A3, manufactured by Kyowa Interface Science Co., Ltd.) at a liquid temperature of 25 ° C. and 60%. It is a value measured by RH.

  In addition, in order to properly maintain the shape in which the ink-jet ink wets and spreads after landing on the substrate, it is preferable to maintain a predetermined liquid property of the ink-jet ink after landing on the substrate. For this purpose, it is preferable to keep the substrate and / or the vicinity of the substrate within a predetermined temperature range. Alternatively, it is also effective to reduce the influence of temperature change by increasing the heat capacity of the table that supports the substrate.

<Color filter and manufacturing method thereof>
A method for producing a color filter by the ink jet method using the colored curable composition of the present invention is not particularly limited. For example, the method described in paragraphs [0114] to [0128] of JP-A-2008-250188 is used. Can be used.

<Use of the color filter of the present invention>
The color filter of the present invention may further have an indium tin oxide (ITO) layer as a transparent conductive film. Examples of the ITO layer forming method include in-line low-temperature sputtering method, in-line high-temperature sputtering method, batch-type low-temperature sputtering method, batch-type high-temperature sputtering method, vacuum deposition method, and plasma CVD method. In order to reduce damage, a low-temperature sputtering method is preferably used.

The color filter of the present invention is suitably used without particular limitation for image display, particularly color image display applications such as liquid crystal displays, organic EL displays, liquid crystal projectors, game machines, mobile terminals such as mobile phones, digital cameras, car navigation systems, and the like. Applicable. Further, it can be suitably used as a color filter for a solid-state imaging device such as a CCD image sensor or a CMOS image sensor used in a digital camera, a digital video camera, an endoscope, a mobile phone, or the like. Particularly, it is suitable for a high-resolution CCD element or CMOS element exceeding 1 million pixels. The configuration of the solid-state imaging device is not limited as long as it includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given. That is, it has a structure in which a transfer electrode made of a photodiode and polysilicon constituting a light receiving area is provided on a support, a color filter layer is provided, and then a microlens is laminated.
The camera system provided with the color filter of the present invention is provided with a camera lens, a cover glass on which an IR cut film is dichroically coated, a microlens, and the like from the viewpoint of light fading of the color material. It is desirable to absorb part or all of UV light of 400 nm or less. Also, the structure of the camera system is preferably such that the oxygen permeability to the color filter is reduced in order to suppress oxidation fading of the colorant. For example, a part or the whole of the camera system Is preferably sealed with nitrogen gas.

  As described above, the colored curable composition, the color filter and the manufacturing method thereof, and the display and solid-state imaging device using the same have been described in detail with reference to various embodiments. Of course, various improvements and modifications may be made without departing from the scope of the present invention.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, equipment, operations, and the like shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the following examples, “%” and “parts” represent “mass%” and “parts by mass” unless otherwise specified, and the molecular weight indicates the weight average molecular weight.

[Synthesis Example 1]
<Synthesis of Exemplified Compound 6>
Exemplified Compound 6 was synthesized according to the following synthesis scheme by the method described below.

<Synthesis of Intermediate (b)>
Sodium thiocyanate (120.5 g, 1.48 mol) and methanol (280 mL) were added, and the internal temperature was raised to 55 ° C. To this, 200 g (1.48 mol) of 1-chloropinacolone (a) was added dropwise over 30 minutes, and after completion of the addition, the reaction was allowed to proceed for 2 hours with the internal temperature being 55 ° C. After completion of the reaction, the internal temperature was cooled to 10 ° C., 250 mL of water was added thereto, and the mixture was stirred at 10 ° C. for 30 minutes, and the crystals were separated by filtration to obtain white crystals of intermediate (b). Yield 218 g (94% yield). Mass spectral result: (m / z) = 158 ([M + 1] ⁺ , 100%).

<Synthesis of Intermediate (c)>
157 g (1 mol) of intermediate (b), 800 mL of toluene, and 28.6 mL of acetic acid were added, and the mixture was heated to an internal temperature of 80 ° C. Diethylamine 104mL was dripped here slowly over 30 minutes, and it was made to react for 3 hours with the internal temperature of 80 degreeC after completion | finish of dripping. After completion of the reaction, the internal temperature was cooled to 30 ° C., 500 mL of water was added, and the toluene layer was washed. Extract from the toluene layer with 1N hydrochloric acid (500 mL × 2 times), neutralize the extract with caustic soda, and extract with ethyl acetate again. The extract was dried over magnesium sulfate and concentrated using a rotary evaporator to obtain a light yellow liquid of intermediate (c). Yield 106 g (50% yield). Mass spectral result: (m / z) = 212 (M ⁺ , 100%).

<Synthesis of Intermediate (d)>
(Synthesis of diazonium salt)
40% nitrosylsulfuric acid 59.8 g (0.188 mol), acetic acid 100 mL, and propionic acid 75 mL were added, and the internal temperature was cooled to 0 ° C. To this, 25 g (0.188 mol) of 2-aminoimidazole-3,4-dicarbonitrile was added in portions and stirred at an internal temperature of 0 to 5 ° C. for 2 hours. (Coupling reaction)
Intermediate (c) 39.9 g (0.188 mol), methanol 350 mL, and sodium acetate 300 g were added to another flask, and the internal temperature was cooled to 0 ° C. To this, the diazonium salt dispersion synthesized as described above was dropped slowly while maintaining the internal temperature at 10 ° C. or less, and after the completion of the dropping, the reaction was carried out at an internal temperature of 0 to 5 ° C. for 1 hour and at room temperature for 1 hour. It was. After completion of the reaction, 400 mL of water was added, and the mixture was stirred at room temperature for 60 minutes. The crystals were separated by filtration and washed with warm water to obtain red crystals of intermediate (d). Yield 62 g (93% yield). Mass spectral result: (m / z) = 357 ([M + 1] ⁺ , 100%).

<Synthesis of Exemplified Compound 6>
In a 300 mL three-necked flask, 14.2 g (0.04 mol) of intermediate (d), 4-vinylbenzyl chloride (0.044 mol), 16.6 g (0.12 mol) of potassium carbonate, 18 g of sodium iodide ( 0.12 mol), 100 mL of N, N-dimethylacetamide and 0.2 mL of nitrobenzene were added and reacted at an internal temperature of 50 ° C. for 2 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, added to 400 mL of water, and extracted with 300 mL of ethyl acetate. The extract was washed with aqueous sodium bicarbonate, dried over magnesium sulfate, added with 5 mg of methoxyphenol, and concentrated to dryness using a rotary evaporator. The obtained residue was suspended and washed with 75 mL of methanol, and the crystals were separated by filtration to obtain metallic glossy green crystals of Exemplary Compound 6. Yield 16.1 g (85% yield). Mass spectral result: (m / z) 473 ([M + 1] ⁺ , 100%). The absorption maximum wavelength in the absorption spectrum of Exemplified Compound 6 in ethyl acetate was 496.4 nm.

<Synthesis of Exemplified Compounds 2, 4, 5, 7-12, 20, 44, 71-73, 75-77, 83, 85, 89, 92, 94, 95, 97, 115, and 117>
Exemplified compounds 2, 4, 5, 7-12, 20, 44, 71-73, 75-77, 83, 85, 89, 92, 94, 95, 97, 115, and 117 are in accordance with the above synthesis examples Was synthesized.
Moreover, exemplary compounds other than exemplary compound 2, 4, 5, 7-12, 20, 22, 44, 71-73, 75-77, 83, 85, 89, 92, 94, 95, 97, 115, and 117 Can be synthesized by a method according to the above synthesis example from a chemical standpoint.

[Synthesis Example 2]
<Synthesis of Exemplified Compound 22 and P21>
Exemplified compounds 22 and P21 were synthesized by the method described below according to the following synthesis scheme.

<Synthesis of Intermediate (f)>
To a 3000 mL three-necked flask, 81.1 g (1.0 mol) of sodium thiocyanate, 800 mL of acetonitrile, and 2 mL of pyridine were added, and the internal temperature was cooled to 5 ° C. in a nitrogen atmosphere. To this, 119 g (1.1 mol) of ethyl chloroformate (compound (e) in the above synthesis scheme) was slowly added dropwise, and after completion of the addition, the mixture was reacted at room temperature for 2 hours. The reaction solution was cooled to an internal temperature of 5 ° C. or lower, and 87.8 g (1.2 mol) of diethylamine was slowly added dropwise at an internal temperature of 10 ° C. or lower. 2000 mL of water was added, and the extract extracted with 1000 mL of ethyl acetate was concentrated by a rotary evaporator. 300 mL of water and 60 mL (1.2 mol) of hydrazine monohydrate were added and reacted at 50 ° C. for 4 hours. The reaction solution was water-cooled, and 300 mL of saturated saline was poured and crystallized. The crystals were separated by filtration and washed thoroughly with water to obtain white crystals of N, N-diethylthiourea as intermediate (f). Yield 87 g (66% yield). Mass spectral result: (m / z) = 133 ([M + 1] ⁺ , 100%).

<Synthesis of Intermediate (g)>
To a 2000 mL three-necked flask was added 66.5 g (0.5 mol) of intermediate (f), 650 mL of isopropyl alcohol, and 77.3 g (0.5 mol) of phenacyl chloride, and the mixture was heated at reflux for 1 hour. Was allowed to cool. Separately, 2000 mL of water was added to a 5000 mL beaker prepared, and the reaction solution was poured into the beaker and neutralized with sodium bicarbonate. Extraction was performed with 1000 mL of ethyl acetate, and the extract was washed with saturated brine and then concentrated with a rotary evaporator to obtain a pale yellow liquid of intermediate (g). Yield 112 g (97% yield). Mass spectral result: (m / z) = 233 ([M + 1] ⁺ , 100%).

<Synthesis of Intermediate (h)>
(Synthesis of diazonium salt)
To a 500 mL three-necked flask, 80 mL of concentrated sulfuric acid was added, and 12.9 g (0.188 mol) of sodium nitrite was carefully added in portions under ice cooling, followed by stirring at an internal temperature of 65 ° C. for 30 minutes. The internal temperature was cooled to 10 ° C. or lower, and 100 mL of acetic acid and 66 mL of propionic acid were slowly added dropwise at an internal temperature of 20 ° C. or lower. The internal temperature was cooled to 5 ° C. or less, 25 g (0.188 mol) of 2-amino-1H-imidazole-4,5-dicarbonitrile was added, and the mixture was stirred at an internal temperature of 0 to 5 ° C. for 1 hour.

(Coupling reaction)
To another flask, 43.6 g (0.188 mol) of the intermediate (g) and 250 mL of methanol were added and cooled to an internal temperature of 0 ° C. Here, the reaction solution of the diazonium salt synthesized as described above was dropped slowly while maintaining the internal temperature at 10 ° C. or less, and after completion of the dropping, the reaction was performed at an internal temperature of 0 to 5 ° C. for 1 hour and at room temperature for 1 hour. I let you. After completion of the reaction, 400 mL of water was added, and the mixture was stirred at room temperature for 60 minutes. The crystals were separated by filtration and washed with hexane / methanol (volume ratio: 8/2) to obtain red crystals of intermediate (h). Yield 67.2 g (95% yield). Mass spectral result: (m / z) = 377 ([M + 1] ⁺ , 100%).

<Synthesis of Exemplified Compound 22>
In a 300 mL three-necked flask, 28.2 g (0.075 mol) of intermediate (h), 13.7 g (0.090 mol) of 4-chloromethylstyrene, 31.1 g (0.225 mol) of potassium carbonate, sodium iodide 33.8 g (0.225 mol) and 180 mL of N, N-dimethylacetamide were added and reacted at an internal temperature of 50 ° C. for 2 hours. The reaction solution was poured into 1000 mL of water, and the precipitated crystals were collected by filtration and then washed with methanol to obtain metallic bright green crystals of Exemplary Compound 22. Yield 30.4 g (82% yield). Mass spectral result: (m / z) = 492 ([M + 1] ⁺ , 100%). The absorption maximum wavelength in the absorption spectrum of Exemplified Compound 22 in ethyl acetate was 521 nm.

<Synthesis of Exemplified Compound P26>
To a 100 mL three-necked flask, 4.00 g (0.0081 mol) of Exemplified Compound 22 obtained above, 0.70 g (0.0081 mol) of methacrylic acid, and 10.97 g of cyclohexanone were added, and the internal temperature was increased under a nitrogen atmosphere. The temperature was raised to 85 ° C. While maintaining the internal temperature at 85 ° C., 112 mg of V-601 (trade name / manufactured by Wako Pure Chemical Industries, Ltd.) was added 3 times in total every 2 hours. After completion of the reaction, the reaction solution was heated to an internal temperature of 90 ° C. and stirred for 2 hours to decompose unreacted V-601. The reaction solution was allowed to cool and reprecipitated with 200 mL of water / methanol (volume ratio: 10/90) to obtain a red powder of Exemplified Compound P26. Yield 4.20 g (89% yield). Molecular weight analysis result (GPC): number average molecular weight Mn = 6,300, weight average molecular weight Mw = 9,870, molecular weight distribution index Mw / Mn = 1.57. The absorption maximum wavelength in the absorption spectrum of Exemplified Compound P26 in ethyl acetate was 520 nm.

<Synthesis of Exemplified Compounds P2, P5, P31, P36, P39, P40, P47, P77, and P81>
Exemplified compounds P2, P5, P31, P36, P39, P40, P47, P77, and P81 were synthesized according to the above synthesis method. In addition, Exemplified Compounds P1, P5, P31, P36, P39, P40, P47, P77, and Exemplified Compounds of P1 to P100 other than P81 should be synthesized from a chemical viewpoint by a method according to the above synthesis example. Can do.

<Evaluation>
The obtained exemplary compounds 2, 4, 5-12, 20, 44, 71-73, 75-77, 83, 85, 89, 92, 94, 95, 115, and 117 in an ethyl acetate solution (concentration 1 Table 1 shows the maximum absorption wavelength of the absorption spectrum at × 10 ⁻⁶ mol / L, optical path length 10 mm). Absorption of the obtained exemplary compounds P2, P5, P26, P31, P36, P39, P40, P47, P77, and P81 in N-methylpyrrolidone solution (concentration 1 × 10 ⁻⁶ mol / L, optical path length 10 mm) Table 1 shows the maximum absorption wavelength of the spectrum.
FIG. 1 shows a solution transmission spectrum of Example Compound 6 synthesized in Synthesis Example 1.

[Example 1]
(1) Preparation of resist solution A (negative type)
Propylene glycol monomethyl ether acetate 5.20 parts Cyclohexanone 52.6 parts Binder 30.5 parts (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate) (molar ratio = 60: 20: 20) ) Average molecular weight 30200 (polystyrene conversion), 41% cyclohexanone solution, dipentaerythritol hexaacrylate 10.2 parts, polymerization inhibitor (p-methoxyphenol) 0.006 parts, fluorosurfactant (trade name: F-475 0.80 parts Photopolymerization initiator: 4-Benzoxolane-2,6-bis (trichloromethyl) -s-triazine (manufactured by TAZ-107 Midori Chemical Co., Ltd.) 0.58 Parts were mixed and dissolved to prepare a resist solution A.

(2) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 0.5% NaOH water, and then washed with water and dehydrated (200 ° C./20 minutes). Next, the resist solution A obtained in the above (1) was applied on a glass substrate washed with a spin coater so that the film thickness after drying was 2 μm, and dried by heating at 220 ° C. for 1 hour, with an undercoat layer. A glass substrate was prepared.

(3) Preparation of colored curable composition • 80 parts of cyclohexanone • Polymerizable compound: 14.0 parts of dipentaerythritol hexaacrylate • Polymerization inhibitor: 0.006 part of p-methoxyphenol • Fluorosurfactant (trade name) : F-475, manufactured by DIC Corporation) 0.80 part. Photopolymerization initiator (TAZ-107 manufactured by Midori Chemical Co., Ltd.) 2.0 parts. Exemplified Compound 95 4.0 parts are mixed and dissolved. A colored curable composition was prepared.

(4) Exposure and development of colored curable composition (image formation)
Using the spin coater so that the film thickness after drying the colored curable composition obtained in (3) above the undercoat layer of the glass substrate with an undercoat layer obtained in (2) above is 0.6 μm. And prebaked at 100 ° C. for 120 seconds.
Next, using an exposure apparatus UX3100-SR (manufactured by USHIO INC.), The coating film was irradiated at a wavelength of 365 nm through a mask having a line width of 2 μm with an exposure amount of 200 mJ / cm ² . After the exposure, development was performed using a developer CD-2000 (manufactured by Fuji Film Electronics Materials Co., Ltd.) at 25 ° C. for 40 seconds. Then, after rinsing with running water for 30 seconds, spray drying was performed. Thereafter, post-baking was performed at 200 ° C. for 15 minutes.
As described above, a pattern suitable for red constituting the color filter was obtained.
FIG. 2 shows the transmission spectrum of the color filter produced in Example 1.

(5) Evaluation Storage stability over time of the colored curable composition prepared above, and heat resistance, light resistance, solvent resistance of a coating film coated on a glass substrate using a dye resist solution, The pattern shape was evaluated as follows. The evaluation results are shown in Table 2 below.

[Storage stability over time]
After the colored curable composition was stored at room temperature for 1 month, the degree of precipitation of foreign matters in the composition was visually evaluated according to the following criteria.
-Criteria-
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

〔Heat-resistant〕
The glass substrate coated with the colored curable composition was placed on a hot plate at 200 ° C. so as to be in contact with the substrate surface and heated for 1 hour, and then the chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.) The color difference (ΔE ^* ab value) before and after heating was measured as an index for evaluating thermal fastness, and evaluated according to the following criteria. A smaller ΔE ^* ab value indicates better heat resistance. The ΔE ^* ab value is a value obtained from the following color difference formula based on the CIE 1976 (L ^* , a ^* , b ^* ) space color system (Japanese Society for Color Science, New Color Science Handbook (Showa 60)) p. 266).
ΔE ^* ab = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2
-Criteria-
○: ΔE ^* ab value <5
Δ: 5 ≦ ΔE ^* ab value ≦ 15
×: ΔE ^* ab value> 15

[Light resistance]
A UV cut filter with a cutoff of 366 nm or less is placed on a glass substrate coated with a colored curable composition, and a xenon lamp is irradiated with 100,000 lux for 20 hours (equivalent to 2 million lux · h), before and after irradiation. The color difference (ΔE ^* ab value) was measured as an index for evaluating light resistance and evaluated according to the following criteria.
The smaller the value of ΔE ^* ab value, the better the light resistance.
-Criteria-
○: ΔE ^* ab value <5
Δ: 5 ≦ ΔE ^* ab value ≦ 12
×: ΔE ^* ab value> 12

[Solvent resistance]
Spectroscopy of the various coating films after post-baking obtained in (4) above was measured (spectrum A). After applying the resist solution A obtained in (1) above to the coating film so as to have a film thickness of 1 μm and pre-baking, CD-2000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) Development was performed under the conditions of 23 ° C. and 120 seconds using the developer, and the spectrum was measured again (spectrum B). The dye residual ratio (%) was calculated from the difference between the spectra A and B, and this was used as an index for evaluating the solvent resistance. This value indicates that the closer to 100%, the better the solvent resistance.
-Criteria-
○: Dye remaining rate> 90%
Δ: 70% ≦ dye residual rate ≦ 90%
X: Dye residual ratio <70%

[Pattern shape]
The development criteria of various coating films after the post-baking obtained in the above (4) are observed with an optical microscope (Olympus Digital Microscope RX-20), and whether or not a fine pattern can be created is as follows. According to the evaluation.
-Criteria-
○: A fine pattern is produced.
Δ: The pattern is fabricated, but the edge of the pattern is not fine.
X: A pattern cannot be produced.

[Examples 2 to 12]
In the preparation of the colored curable composition of Example 1 (3), a pattern was formed in the same manner as in Example 1 except that the exemplified compound 95 was changed to the pigment described in Table 2 (but equivalent mass), and further Similar evaluations were made. The evaluation results are shown in Table 2 below. The dyes used in Comparative Examples 1 and 2 are shown below.

[Comparative Examples 1-2]
In the preparation of the colored curable composition of Example 1 (3), except that the exemplified compound 95 was changed to the following comparative dyes 1-2 (Comparative Examples 1-2) (however, the same mass), as in Example 1. Then, a pattern was formed and the same evaluation was performed. The evaluation results are shown in Table 2 below together with the results of the examples.

As shown in Table 2, Examples 1 to 12 using the coloring matter according to the present invention are all excellent in the storage stability of the colored curable composition over time, and this colored curable composition is used. The pattern thus formed exhibited good heat resistance, light resistance, and solvent resistance. On the other hand, Comparative Example 1 is inferior in storage stability of the colored curable composition, and the pattern formed using the colored curable composition in Comparative Example 1 is inferior in heat resistance, light resistance, and solvent resistance. Also, the pattern shape was inferior and the edges were not fine. Moreover, the pattern formed using the colored curable composition of Comparative Example 2 had poor light resistance, poor solvent resistance, and poor pattern shape, and the edges were not fine.
As shown in Table 2, in the present invention (Examples 1 to 12), Examples 1 to 5 using the azo dye compound represented by the general formula (2) were particularly excellent in heat resistance. In addition, the specific dye compound of the present invention has a very high solubility in various organic solvents including cyclohexane used in the examples (for example, ethyl lactate having higher safety). It was also effective in reducing the load.
Moreover, Examples 10-12 using the compound containing at least one repeating unit represented by the general formula (P) are good in all of stability over time, heat resistance, light resistance, solvent resistance, and pattern formability. It was a result.

比較色素２：Ｃ．Ｉ．アシッド・レッド８７

Comparative dye 2: C.I. I. Acid Red 87

[Examples 13 to 21, Comparative Examples 3 and 4, and Examples 22 to 30, Comparative Examples 5 and 6]
Using the colored curable compositions used in Examples 1 to 12 and Comparative Examples 1 and 2, color filters were prepared by the following procedure, and color transfer evaluation was performed as Examples 13 to 21 and Comparative Examples 3 and 4. Carried out.
At the same time, a color filter was prepared without performing the ultraviolet irradiation step after the development step, and Examples 22 to 30 and Comparative Examples 5 and 6 were carried out to evaluate the color transfer.

-Fabrication of single color filter-
Using the colored curable compositions used in Examples 1 to 9 and Comparative Examples 1 and 2 on the glass substrate with the undercoat layer (2) prepared in Example 1, the dry film thickness was 1 μm. Coating was performed using a spin coater and prebaked at 100 ° C. for 120 seconds to form a colored film. With respect to this colored film, 7.0 [mu] m square pixels are respectively provided by an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) through a mask pattern in which an area of 4 mm × 3 mm on the substrate is 200 [ mJ / cm ² ] and an exposure of 1200 mW / cm ² (integrated irradiation illuminance). After exposure, paddle development was performed at 23 ° C. for 60 seconds using a developer (trade name: CD-2000, 60%, manufactured by Fuji Film Electronics Materials Co., Ltd.) to form a pattern. Subsequently, it was rinsed with running water for 20 seconds and then spray-dried. Thereafter, as an ultraviolet irradiation step after the development step, the entire glass substrate on which the pattern was formed was irradiated with 10,000 [mJ / cm ² ] ultraviolet rays using a high-pressure mercury lamp (Ushio Electric Co., Ltd. UMA-802-HC552FFAL). . After irradiation, post-baking treatment was performed on a hot plate at 220 ° C. for 300 seconds to form a colored pattern on the glass substrate. In addition, the wavelength light of 275 nm or less contained in the irradiation light from a high pressure mercury lamp is 10%.
As described above, monochromatic color filters of Examples 13 to 21 and Comparative Examples 3 and 4 were produced. Moreover, the monochrome color filter of Examples 22-30 and the comparative examples 5 and 6 was produced, without performing the ultraviolet irradiation after a image development process.

-Color transfer evaluation-
Apply the CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd .; foundation clearing agent) to the colored pattern forming surface of the color filter produced as described above so that the dry film thickness is 1 μm, and let it dry. After forming the transparent film, heat treatment was performed at 200 ° C. for 5 minutes. After the heating, the absorbance of the transparent film adjacent to the colored pattern was measured with a microspectrophotometer (LCF-1500M manufactured by Otsuka Electronics Co., Ltd.). The ratio [%] of the absorbance value of the obtained transparent film to the absorbance of the colored pattern similarly measured before heating was calculated and used as an index for evaluating the color transfer.
-Criteria-
Color transfer to adjacent pixels (%)
A: Color transfer to adjacent pixels <1%
○: 1% <color transfer to adjacent pixels ≦ 10%
Δ: 10% ≦ color transfer to adjacent pixel ≦ 30%
×: Color transfer to adjacent pixels> 30%

[Example 31 to Example 39]
-Fabrication of color filters for solid-state image sensors-
(Preparation of silicon wafer substrate with undercoat layer)
A 6-inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, on this silicon wafer, the resist solution A prepared in (1) of Example 1 was applied to a dry film thickness of 1.0 μm, and further dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. And a silicon wafer substrate with an undercoat layer was obtained.

(Preparation of color filter pattern for solid-state image sensor)
Each colored curable composition used in Examples 1 to 9 was applied on the undercoat layer of the obtained silicon wafer substrate with the undercoat layer so that the dry film thickness of each coating film was 0.8 μm, A photocurable coating film was formed. And it heat-processed for 120 second (prebaking) using the 100 degreeC hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.), an exposure dose of 100 mJ / cm in the range of 100 to 2500 mJ / cm ² through an island pattern mask having a pattern of 1.2 μm square at a wavelength of 365 nm. Irradiation was carried out while changing by ² cm ² . Thereafter, the silicon wafer substrate on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics Co., Ltd.), and 60% CD-2000 ( Paddle development was performed at 23 ° C. for 60 seconds using FUJIFILM Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

The silicon wafer substrate on which the colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 rpm by a rotation device, and pure water is ejected from above the rotation center from the ejection nozzle. It was supplied as a shower and rinsed, and then spray-dried.
Each pattern image obtained using each colored curable composition used in Examples 1 to 9 was square and the cross-sectional shape was rectangular. It was suitable for a solid-state image sensor and showed a good profile.

[Examples 40 and 41]
Next, a color filter was produced by an ink jet method. First, as preparation for preparing a substrate provided with partition walls, a pigment dispersion K in which carbon black used for the partition wall forming composition (K1) was dispersed was prepared with the following composition.

<Composition of Pigment Dispersion K>
・ Carbon black (Nippex 35 manufactured by Degussa) 13.1%
Dispersant (Compound B1 having the following structure) 0.65%
-Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.72%
Propylene glycol monomethyl ether acetate 79.53%

<Preparation of partition wall forming composition (K1)>
Table 4 shows the composition of the partition wall forming composition (K1).
Pigment dispersion K and propylene glycol monomethyl ether acetate are mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and further stirred, methyl ethyl ketone, binder 2, hydroquinone monomethyl ether, DPHA liquid, 2 , 4-Bis (trichloromethyl) -6- [4 ′-(N, N-bisdiethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine, surfactant 1 at 25 ° C. (± 2 ° C.) in this order and obtained by stirring at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.).

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27%
・ Propylene glycol monomethyl ether acetate 73%

<DPHA solution>
Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76%
・ Propylene glycol monomethyl ether acetate 24%

<Surfactant 1>
・ The following structure 1 30%
・ Methyl ethyl ketone 70%

<Formation of partition walls>
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the above-mentioned partition wall-forming composition K1 using a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. Was applied. Subsequently, a part of the solvent was dried with a VCD (vacuum drying apparatus, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then prebaked at 120 ° C. for 3 minutes to form a partition wall having a film thickness of 2.3 μm. A substrate having a forming layer was obtained.
Next, with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the distance between the exposure mask surface and the partition wall formation layer is set to 200 μm with the substrate and the mask standing vertically. The pattern exposure was performed under a nitrogen atmosphere with an exposure amount of 300 mJ / cm ² to a partition wall width of 20 μm and a space width of 100 μm.

Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the partition wall forming layer, a KOH developer (containing nonionic surfactant, trade name: CDK-1, Fuji Film Electronics Materials) Manufactured by Co., Ltd., 100 times diluted) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultra-high pressure cleaning nozzle to remove the residue, and the surface side on which the partition wall forming layer of the substrate was formed at an exposure amount of 2500 mJ / cm ^{2 in} the atmosphere The film was post-exposed and heated in an oven at 240 ° C. for 50 minutes to obtain a stripe-shaped partition wall having an opening having a thickness of 2.0 μm, an optical density of 4.0, and a width of 100 μm.

(Ink-repellent plasma treatment)
The substrate on which the barrier ribs were formed was subjected to ink repellent plasma treatment under the following conditions using a cathode coupling parallel plate type plasma treatment apparatus.
Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

(Preparation of red (R) ink)
The ingredients listed in Table 5 were mixed and stirred for 1 hour. Thereafter, filtration was performed under reduced pressure using a microfilter manufactured by Fuji Film Co., Ltd. having an average pore diameter of 0.25 μm, thereby preparing red ink liquids (ink R-1 and ink R-2) of the present invention.

Details of the materials used in the preparation of the red (R) ink are shown below.
-Dye: exemplary compound 99 of the compound represented by the general formula (2)
Polymerizable compound (Nippon Kayaku Co., Ltd. (KAYARAD DPCA-60)): Caprolactone-modified dipentaerythritol hexaacrylate KF-353 (manufactured by Shin-Etsu Silicone): Polyether-modified silicone oil Polymerization initiator: Azobis (cyclohexane- 1-carbonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) V-40)

(Measurement of viscosity and surface tension)
While adjusting the temperature of the obtained ink to 25 ° C., the viscosity was measured under the following conditions using an E-type viscometer (RE-80L) manufactured by Toki Sangyo Co., Ltd.
(Measurement condition)
-Rotor used: 1 ° 34 'x R24
・ Measurement time: 2 minutes ・ Measurement temperature: 25 ° C

The surface tension meter (FACE) manufactured by Kyowa Interface Science Co., Ltd. was maintained with the temperature of the obtained ink adjusted to 25 ° C.
Surface tension was measured using SURFACE TENSIOMETER CBVB-A3).

(Contrast measurement method)
As a backlight unit, a cold cathode tube light source (light source emitting light having a wavelength spectrum distribution shown in FIG. 3) provided with a diffusion plate is used, and a monochromatic substrate between two polarizing plates (POLAX-15N manufactured by Luceo) And the Y value of the chromaticity of the light that passes when the polarizing plate is installed in parallel Nicol is divided by the Y value of the chromaticity of the light that passes when installed in crossed Nicol. A color luminance meter (BM-5A manufactured by Topcon Co., Ltd.) was used for the measurement of chromaticity.
The measurement angle of the color luminance meter was set to 1 °, and the measurement was performed with a visual field of 5 mm on the sample. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 400 cd / m ² with no sample installed.

The monochromatic substrate was produced by the following method. Same as color filter formation by forming a solid film on the glass substrate by the ink jet method or the spin coat method using one color ink among the R inks (ink R-1, ink R-2) constituting the color filter. Thus, pre-baking (preheating) (temperature 100 ° C., 2 minutes) and post-baking (post-heating) (temperature 220 ° C., 30 minutes) were performed to form a monochromatic substrate having a thickness of 2 μm.
When the contrast of the monochromatic substrates (six types) obtained above was measured, a value of 50000 or more was obtained with any monochromatic substrate.

(ITO layer production)
Next, using a sputtering apparatus on the monochromatic substrate obtained above, ITO (indium tin oxide) is sputtered at a film surface temperature of 200 ° C. for 15 minutes to form an ITO film having a thickness of 1500 mm. A color filter substrate was produced.

(Change in spectral characteristics before and after ITO sputtering)
Before and after ITO sputtering, a spectral transmittance curve in a wavelength range of 400 nm to 700 nm was obtained using an ultraviolet-visible absorption spectrometer (V-570 manufactured by JASCO Corporation). If the change in spectral transmittance at the maximum peak before and after sputtering is small, it means that the heat resistance is good. It was found that the spectrum shape of the prepared substrate hardly changed before and after ITO sputtering, and it had high heat resistance.

[Comparative Examples 7 and 8]
(Preparation of pigment dispersion)
Pigment C.I. I. Pigment Red 177 (manufactured by Ciba Specialty Chemicals: Chromophthal Red A2B) 17.5 parts, pigment dispersant (compound B1) 2.5 parts, and solvent (1,3-butanediol diacetate) (hereinafter 1 , 3-BGDA) 80 parts, premixing, motor mill M-50 (manufactured by Eiger Japan), using 0.65 mm diameter zirconia beads at a filling rate of 80%, peripheral speed 9 m / S for 25 hours to prepare a pigment dispersion for R (R-177).

  In the pigment dispersion for R (R-177), the pigment is C.I. I. Pigment Red 254 (manufactured by Ciba Specialty Chemicals): Ir pigment dispersion (R-254) in the same manner as R pigment dispersion (R-177), except that it was changed to Irgaphor Red B-CF. ) Was prepared. In addition, as a result of measuring the number average particle diameter of this pigment dispersion using Nikkiso Nanotrack UPA-EX150, all were 50 nm.

(Preparation of ink used in Comparative Examples 7 and 8)
As Comparative Examples 7 and 8, comparative inks R-3 and R-4 having the compositions shown in Table 6 were prepared using the pigment dispersions (R-177) and (R-254), respectively. . The materials used are as follows.
・ Solvent: Propylene glycol monomethyl ether acetate (abbreviated as MMPGAC ・ Polymerizable compound: KAYARAD DPS100 manufactured by Nippon Kayaku Co., Ltd.
Polymerizable compound: KAYARAD TMPTA manufactured by Nippon Kayaku Co., Ltd.
-Surfactant: The above-mentioned surfactant 1
Polymerization initiator: Azobis (cyclohexane-1-carbonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) V-40)

(Method for producing color filter for evaluation)
Using the inks R-1 to R-4 prepared above, an inkjet printer DMP manufactured by Fuji Film Dimatix is placed in the area (the concave part surrounded by the convex part) divided by the partition on the substrate obtained above. Using -2831, discharging was performed, and then heating was performed in a 100 ° C. oven for 2 minutes. Next, the monochromatic color filter was produced by leaving still for 30 minutes in 220 degreeC oven.

(Ink storage stability evaluation)
Each ink prepared above is stored in a thermostatic chamber at 50 ° C., the viscosity after 30 days is measured, and the difference (%) from the value immediately after ink preparation [(viscosity after 30 days−viscosity immediately after preparation) / preparation. Evaluation was performed according to [Viscosity immediately after]. Evaluation criteria were classified as follows.
A: Difference from the viscosity immediately after ink preparation is less than 10% B: Difference from viscosity immediately after ink preparation is 10% or more and less than 20% Δ: Difference from viscosity immediately after ink preparation is 20% or more and less than 30% ×: The difference from the viscosity immediately after ink preparation is 30% or more

(Continuous discharge stability evaluation)
Using each of the inks prepared above, the ejection stability was evaluated. The evaluation method was performed using an inkjet printer DMP-2831, manufactured by Fujifilm Dimatix, a head cartridge with a droplet ejection amount of 10 pL, and a droplet ejection frequency of 10 kHz, and the state when continuously ejected for 30 minutes was observed. Evaluation criteria were classified as follows.
A: Continuous discharge is possible without problems.
◯: Slight non-ejection, ejection disturbance, etc. are observed during ejection, but it returns during ejection and there is almost no problem.
Δ: Non-discharge or discharge disturbance occurs during discharge, and does not return during discharge, but returns to normal by maintenance.
X: Non-discharge or discharge disturbance occurs during discharge, normal discharge cannot be performed, and discharge does not return even during maintenance.
Maintenance includes purging with DMP-2831 (pressurizing ink in the head and forcibly ejecting ink from the nozzle) and blotting (with the head nozzle surface slightly touching the cleaning pad and sucking ink from the nozzle surface) did.

(Evaluation of ejection stability after pause)
Using each of the inks prepared above, the ejection stability was evaluated. The evaluation method is the same as the continuous discharge stability evaluation, using an inkjet printer DMP-2831, manufactured by Fujifilm Dimatix, and a head cartridge with a droplet ejection amount of 10 pL, and ejecting once for 5 minutes at a droplet ejection frequency of 10 kHz. The state when the discharge was started again under the same conditions was observed. Evaluation criteria were classified as follows.
A: Discharge is possible without any problems at the same time as the droplet ejection instruction.
○: Immediately after the droplet ejection instruction, a slight non-ejection, ejection disturbance, etc. are observed, but it returns during ejection and there is almost no problem.
Δ: Non-ejection, ejection disturbance, and does not return during ejection, but returns to normal by maintenance.
X: Non-ejection and ejection disturbance occur, normal ejection cannot be performed, and ejection does not return to a normal level even during maintenance.
Maintenance includes purging with DMP-2831 (pressurizing ink in the head and forcibly ejecting ink from the nozzle) and blotting (with the head nozzle surface slightly touching the cleaning pad and sucking ink from the nozzle surface) did.

(Heat resistance evaluation)
Each color filter prepared above was placed in an oven heated to 230 ° C. and allowed to stand for 1 hour, and then the hue was measured. For the measurement of hue, UV-560 (manufactured by JASCO Corporation) was used, and ΔE ^* ab before and after the evaluation was evaluated as ○ when less than 5. ΔE ^* ab was 5 or more and less than 15 and Δ, and ΔE ^* ab was 15 or more and x.

(Chemical resistance evaluation)
Each color filter produced above was immersed in the chemicals to be evaluated (N-methylpyrrolidone, 2-propanol, 5% sulfuric acid aqueous solution, 5% sodium hydroxide aqueous solution) for 20 minutes, and the hue before and after that was measured. For the measurement of hue, UV-560 (manufactured by JASCO Corp.) was used, and ΔE ^* ab was less than 5 as ◯. ΔE ^* ab was 5 or more and less than 15 and Δ, and ΔE ^* ab was 15 or more and x. The method for evaluating ΔE ^* ab is the same as described above.

  Table 7 summarizes the evaluation results of the inkjet ink and the color filter.

As shown in Table 7, the ink-jet ink using the pigment having a specific structure of the present invention was excellent in storage stability and discharge stability. In addition, the color filter manufactured using the ink-jet ink described in the present invention had excellent chemical resistance and heat resistance comparable to those obtained when using an ink using a pigment.
On the other hand, Comparative Examples 7 and 8 using an ink using a pigment were inferior in ejection stability after a pause and lacked in stability of continuous ejection, and lacked practicality.

Claims (17)

A colored curable composition containing at least one selected from the group consisting of compounds represented by the following general formula (1) and tautomers thereof, and at least one polymerizable compound.

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. R ¹¹ and R ¹² , and R ¹⁵ and R ¹⁶ may be independently bonded to each other to form a ring.) The colored curable composition according to claim 1, wherein the general formula (1) is the following general formula (2).

(In General Formula (2), R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁶ , R ³¹ , R ³² , R ³⁴ , R ³⁵ , and R ³⁶ are each independently a hydrogen atom or monovalent substitution. L ¹ represents a divalent linking group, and R ²¹ and R ²² , R ²⁵ and R ²⁶ , R ³¹ and R ³² , and R ³⁵ and R ³⁶ are each independently bonded to each other to form a ring. (It may be formed.) The colored curable composition according to claim 1 or 2, wherein the compound represented by the general formula (1) is a compound including at least one repeating unit represented by the following general formula (P).

(In General Formula (P), R ^P1 , R ^P2 and R ^P3 each independently represent a hydrogen atom or a monovalent substituent, and * represents one hydrogen atom removed from General Formula (1). Represents a bond that binds to a residue, and n represents an integer of 1 to 100.)   The colored curable composition according to any one of claims 1 to 3, wherein the polymerizable compound is a compound having two or more ethylenically unsaturated groups in the molecule.   A color resist comprising the colored curable composition according to any one of claims 1 to 4 and used for forming a colored pixel by a photolithography method.   An inkjet ink comprising the colored curable composition according to any one of claims 1 to 4 and used for forming colored pixels by an inkjet method.   A color filter using the colored curable composition according to any one of claims 1 to 4.   A step of applying a colored curable composition according to any one of claims 1 to 4 on a support to form a colored layer, and a step of exposing the colored layer through a mask. And a step of forming a pattern by development after the exposure.   The method for producing a color filter according to claim 8, further comprising a step of irradiating ultraviolet rays after the step of forming a pattern by the development.   Pixel formation which forms a colored pixel by ejecting the colored curable composition according to any one of claims 1 to 4 by an ink-jet method into a recess defined by a partition formed on a substrate. A method for producing a color filter having a process.   A solid-state imaging device comprising the color filter according to claim 7.   An image display device comprising the color filter according to claim 7.   A liquid crystal display comprising the color filter according to claim 7.   An organic EL display comprising the color filter according to claim 7. A dye compound represented by the following general formula (2) and tautomers thereof.

(In General Formula (2), R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁶ , R ³¹ , R ³² , R ³⁴ , R ³⁵ , and R ³⁶ are each independently a hydrogen atom or monovalent substitution. L ¹ represents a divalent linking group, and R ²¹ and R ²² , R ²⁵ and R ²⁶ , R ³¹ and R ³² , and R ³⁵ and R ³⁶ are each independently bonded to each other to form a ring. (It may be formed.) A dye compound containing at least one repeating unit represented by the following general formula (P) and tautomers thereof.

In the general formula (P), R ^P1 , R ^P2 , and R ^P3 each independently represent a hydrogen atom or a monovalent substituent, and * represents a residue obtained by removing one hydrogen atom from the following general formula (1) Represents a group, and n represents an integer of 1 to 100. )

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. R ¹¹ and R ¹² , and R ¹⁵ and R ¹⁶ may be independently bonded to each other to form a ring.)   The dye compound and tautomers thereof according to claim 16, wherein the dye compound has an acid group in a range of 25 mgKOH / g to 200 mgKOH / g.

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