JP5680359B2 - Colored curable composition, color resist, color filter, method for producing color filter, and solid-state imaging device and image display device provided with color filter - Google Patents

Description

  The present invention relates to a colored curable composition, a color resist, a color filter, a method for producing a color filter, and a solid-state imaging device and an image display device provided with the color filter.

In recent years, with the development of personal computers and large-screen liquid crystal televisions, the demand for liquid crystal displays (LCDs), especially color liquid crystal displays, has increased significantly, and the spread of organic EL displays is also awaited for achieving higher image quality. . On the other hand, the demand for solid-state imaging devices such as CCD image sensors is greatly increasing due to the spread of digital cameras, camera-equipped mobile phones and the like.
Color filters are used as key devices for these displays and optical elements, and there are increasing demands for higher image quality and cost reduction for the color filters.

Color filters used in image display devices and solid-state image sensors usually have a coloring pattern of three primary colors of red (R), green (G), and blue (B), and color passing light It plays the role of decomposing into the three primary colors.
The colorant used for the color filter is required to have the following properties. 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 in a solid-state image sensor. It is necessary to have no problem, fastness under environmental conditions to be used, for example, good heat resistance, light resistance, moist heat resistance, etc., a large molar extinction coefficient and a thin film.

Conventionally, a color filter has been prepared using a pigment as a colorant, but the use of a dye instead of the pigment has been studied. When using a dye, the following points are particularly problematic.
(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.
In particular, when using a photolithographic method for producing a color filter,
(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) Dyes often interact with other components in the colored curable composition, and it is difficult to adjust the solubility (developability) of 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 been difficult to form a coloring pattern that is fine and thin for a high-definition color filter and has excellent fastness properties 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.

  In addition, in a colored curable composition containing a dye, when heat treatment is performed after film formation, a phenomenon in which color transfer is likely to occur between adjacent colored patterns having different hues or between stacked and overlapping layers is likely to occur. It has been pointed out. In addition to color transfer, patterns are more likely to be peeled off in low-exposure areas due to reduced sensitivity, 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 methods for solving such problems, 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 1). 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 2). Furthermore, a method for producing a color filter is disclosed in which light irradiation is performed between the development process and the heat treatment to prevent shape deformation of the color filter (see, for example, Patent Document 3). Moreover, the method of solving these problems by polymerizing a pigment | dye is disclosed (for example, refer patent documents 4-6).
However, these methods do not sufficiently solve the problems of fastness, color transfer, and pattern formability, and further improvements are required.

Japanese Patent Laying-Open No. 2005-316012 Japanese Patent No. 3309514 JP 2006-258916 A JP 2007-139906 A JP 2007-138051 A Japanese Patent No. 3736221

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, a first object of the present invention is to provide a colored curable composition and a color resist excellent in light resistance and heat resistance.
A second object of the present invention is to provide a color filter excellent in heat resistance and light resistance, and a method for producing the color filter.
A third object of the present invention is to provide a solid-state imaging device and an image display device (liquid crystal display, organic EL display, etc.) provided with a color filter having excellent heat resistance and light resistance.

  As a result of examining the various dyes in detail, the present inventors have polymerized specific dyes and further added the polymerizable group to the solvent solubilized while maintaining a good hue and a high extinction coefficient. In addition, it is possible to provide a cured film that is excellent in lightness, fastness such as heat resistance, light resistance, etc., has high solvent resistance, and can reduce color transfer, and if necessary, an alkali-soluble group is introduced into the dye multimer. Thus, the inventors have obtained the knowledge that a cured film having excellent pattern formability (low concentration dependency of alkali developer) can be provided, and the present invention has been achieved based on such knowledge.

Specific means for achieving the above object are as follows.
<1> (A) has a A zone dye and group derived from a dye selected from dipyrromethene dye, further dye multimer having a polymerizable group, and (B) a colored curable composition containing a polymerizable compound It is.
<2> The coloring according to <1>, wherein the dye multimer includes, as a repeating unit, a structural unit having a polymerizable group and a structural unit having a group derived from a dye selected from an azo dye and a dipyrromethene dye. It is a curable composition.
<3> The colored curable composition according to <2>, wherein the dye multimer contains 1% by mass or more of a structural unit having a polymerizable group.
< 4 > The colored curable composition according to any one of <1> to <3>, wherein the polymerizable group is an ethylenically unsaturated group.

< 5 > The colored curing according to any one of <1> to < 4 >, wherein the dipyrromethene dye is a dipyrromethene dye in which a compound represented by the following general formula (1) is coordinated to a metal atom or a metal compound. Composition.

In the general formula (1), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Represents.

< 6 > The colored curable composition according to < 5 >, wherein the dipyrromethene dye is a dipyrromethene dye represented by the following general formula (C).

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

< 7 > The colored curable composition according to any one of <1> to < 6 >, further comprising (C) a polymerization initiator and (D) a solvent.
< 8 > A color resist comprising the colored curable composition according to any one of <1> to < 7 > and used for forming colored pixels by a photolithography method.

< 9 > A color filter using the colored curable composition according to any one of <1> to < 7 >.
< 10 > A colored layer forming step of forming a colored layer by applying the colored curable composition according to any one of <1> to < 7 > on a support, and a mask for the colored layer Through a pattern-like exposure to form a latent image, and a color filter manufacturing method comprising developing a colored layer on which the latent image is formed to form a pattern.
< 11 > The method for producing a color filter according to < 10 >, further including an ultraviolet irradiation step of irradiating the formed pattern with ultraviolet rays after the developing step.

< 12 > A solid-state imaging device including the color filter according to < 9 >.
< 13 > An image display device including the color filter according to < 9 >.

According to the present invention, a colored curable composition and a color resist excellent in light resistance and heat resistance can be provided.
In addition, a color filter excellent in heat resistance and light resistance and a method for producing the color filter can be provided.
Furthermore, a solid-state image sensor and an image display device (a liquid crystal display, an organic EL display, etc.) provided with a color filter excellent in heat resistance and light resistance can be provided.

It is a figure which shows an example of the solution transmission spectrum in the ethyl acetate of the dye monomer which concerns on a present Example. It is a figure which shows an example of the spectral characteristic of the color filter which concerns on a present Example.

  Hereinafter, the colored curable composition, the color resist, the color filter, the method for producing the color filter, the solid-state imaging device, and the image display device of the present invention will be described in 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 (A) a polymerizable group and at least one dye multimer comprising a group derived from a dye selected from an azo dye and a dipyrromethene dye, and (B) a polymerizable compound. Containing at least one of the following.

The colored curable composition of the present invention is characterized by being cured by heat, light, or both, and further preferably contains (C) a polymerization initiator and (D) a solvent, if necessary. Other components such as a binder and a crosslinking agent may be included.
Hereinafter, the components contained in the colored curable composition of the present invention will be described in detail.

(A) Dye Multimer The colored curable composition of the present invention comprises a dye multimer (hereinafter simply referred to as “polymerizable group-containing”) containing a polymerizable group and a group derived from a dye selected from an azo dye and a dipyrromethene dye. At least one kind of “pigment multimer”. The polymerizable group-containing dye multimer functions as, for example, a colorant in the colored curable composition of the present invention.

Since the polymerizable group-containing dye multimer is a dye multimer containing a group derived from a dye selected from azo dyes and dipyrromethene dyes, it has a good hue and a high extinction coefficient, and is colored and cured according to the present invention. Even when the composition is thinned, it can form a cured film having excellent color purity.
The group derived from the azo dye or dipyrromethene dye contained in the polymerizable group-containing dye multimer may be one kind or two or more kinds.

In addition, since the polymerizable group-containing dye multimer has a polymerizable group, the colored curable composition of the present invention is excellent in light resistance, heat resistance, and solvent resistance even when it is thinned. A cured film with little transfer and good pattern formability can be formed.
The polymerizable group contained in the polymerizable group-containing dye multimer may be one type or two or more types.
Examples of the polymerizable group include an ethylenically unsaturated group (for example, methacryl group, acrylic group, styryl group, etc.), a cyclic ether group (for example, epoxy group, oxetanyl group, etc.) and the like. Among these, an ethylenically unsaturated group is preferable from the viewpoint of heat resistance and solvent resistance after polymerization.

The polymerizable group-containing dye multimer includes a constituent unit having a polymerizable group and a constituent unit having a group derived from a dye selected from an azo dye and a dipyrromethene dye (hereinafter referred to simply as “a constituent having a group derived from a dye”). It is preferable to include as a repeating unit.
The polymerizable group-containing dye multimer may contain a constituent unit having a polymerizable group and a constituent unit other than a constituent unit having a group derived from a dye.
In the polymerizable group-containing dye multimer, from the viewpoint of thinning the color filter, it is preferable to include 60 mass% to 99 mass% of a structural unit having a group derived from the dye in a mass ratio of 70 mass%. It is more preferable to contain -97 mass%, and it is further more preferable to contain 80 mass%-95 mass%.
Further, from the viewpoint of heat resistance and solvent resistance, the structural unit having a polymerizable group is preferably contained in an amount of 1% by mass to 40% by mass, more preferably 3% by mass to 30% by mass. More preferably, the content is 20% by mass to 20% by mass.

  The structural unit having a group derived from the dye is, for example, radical polymerization of a dye compound in which a polymerizable group (for example, acryloxy group, methacryloxy group, styryl group, etc.) is introduced into an azo dye skeleton or a dipyrromethene dye skeleton. And can be introduced into the polymerizable group-containing dye multimer. Alternatively, a dye compound in which a polycondensation or polyaddition reaction group is introduced into an azo dye skeleton or a dipyrromethene dye skeleton may be reacted with a polyfunctional crosslinking agent to be introduced into the polymerizable group-containing dye multimer. it can.

The structural unit having a polymerizable group can be introduced into the polymerizable group-containing dye multimer by the following method, for example.
That is, a structure in which a multimer is obtained by copolymerization of the dye compound and a copolymer component having no dye skeleton (for example, methacrylic acid, acrylic acid, hydroxyethyl methacrylate, etc.), and then derived from the copolymer component By adding a polymerizable compound having a group that reacts with the unit (for example, glycidyl methacrylate, methacryloxyethyl isocyanate, etc.), a structural unit having a polymerizable group can be introduced.
In addition, when the dye compound has a reactive group, it is derived from the structural unit having a polymerizable group and the dye by reacting the polymerizable compound having a group that reacts with the structural unit having the group derived from the dye. It is good also as a structural unit which served as the structural unit which has group.
In the dye compound, a polymerizable group different from the polymerizable group for multimerization of the dye compound is introduced into the azo dye skeleton or the dipyrromethene dye skeleton, and the dye compound is polymerized to be polymerized. It is also possible to obtain a functional group-containing dye multimer.
Furthermore, after polymerizing a dye compound or a copolymer component that does not have a dye skeleton in which a group that becomes a precursor of a polymerizable group is introduced, various reactions (for example, treatment with an alkaline solution) are performed to obtain a polymerizable group. A structural unit having a polymerizable group can be formed by generating a polymerizable group from a group that becomes a precursor of the above.

  Hereinafter, the azo dye and dipyrromethene dye, the structural unit having a group derived from the dye, and the structural unit having a polymerizable group will be described in detail.

(1) Azo dye and dipyrromethene dye The azo dye and dipyrromethene dye are not particularly limited, but the following azo dyes or dipyrromethene dyes are suitable.

(1-1) Dipyrromethene Dye A dipyrromethene dye in which a compound represented by the following general formula (1) is coordinated to a metal atom or a metal compound is preferably used in terms of light resistance and heat resistance.

In the general formula (1), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Represents.

R ^{1 to} R ⁶ each independently represent a hydrogen atom or a monovalent substituent, and examples of the monovalent substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl A group (preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl A group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, for example, a vinyl group, an allyl group, 3-buten-1-y Group), an aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group), a heterocyclic group (preferably having 1 to 32 carbon atoms, more preferably Is a C1-C18 heterocyclic group, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1 -Pyrazolyl group, benzotriazol-1-yl group), silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxy group, cyano group, nitro group, alkoxy group (preferably having 1 to 1 carbon atoms) 8, more preferably an alkoxy group having 1 to 24 carbon atoms, such as a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a t-butoxy group, a dodecyloxy group, or a cycloalkyl In the case of an oxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group), an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenoxy group, 1- A naphthoxy group), a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy group, 2-tetrahydropyranyloxy group) Group), a silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, For example, a trimethylsilyloxy group, t-butyldimethylsilyloxy group, diphenylmethylsilyloxy group), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group, A pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an ethoxycarbonyloxy group, t- In the case of a butoxycarbonyloxy group and a cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group, an aryloxycarbonyloxy group (preferably an aryl having 7 to 32 carbon atoms, more preferably an aryl having 7 to 24 carbon atoms) A xycarbonyloxy group such as a phenoxycarbonyloxy group, a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dimethylcarbamoyloxy group). Group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms). Sulfamoyloxy group, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group),

An alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group), an arylsulfonyloxy A group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, more preferably 1 carbon atom). To 24 acyl groups, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably 2 carbon atoms). To 24 alkoxycarbonyl groups, for example A xoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), an aryloxycarbonyl group (preferably having 7 to 32 carbon atoms, More preferably, it is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group, and a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a carbamoyl group. N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N-dicyclohexyl A carbamoyl group), an amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, 2- An ethylhexylamino group, a cyclohexylamino group), an anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24, for example, an anilino group or an N-methylanilino group), a heterocyclic amino group (preferably A heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 4-pyridylamino group), a carbonamido group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms). , For example, acetamide group, benzamide group, tetradecanamide group, pivaloylamide group, cyclohexaneamide group) Ureido groups (preferably ureido groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido group, N, N-dimethylureido group, N-phenylureido group), imide groups (preferably An imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, for example, an N-succinimide group or an N-phthalimide group) or an alkoxycarbonylamino group (preferably having 2 to 48 carbon atoms, more preferably 2 to 2 carbon atoms). 24 alkoxycarbonylamino groups, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having a carbon number) 7 to 32, more preferably 7 to 7 carbon atoms 4 aryloxycarbonylamino group, for example, phenoxycarbonylamino group), sulfonamido group (preferably 1-48 carbon atoms, more preferably 1-24 carbon sulfonamido groups, for example, methanesulfonamido group, A butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group, a cyclohexanesulfonamide group), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). For example, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms azo group) And, for example, phenylazo group, 3-pyrazolylazo group),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably having 6 to 48 carbon atoms). More preferably, it is an arylthio group having 6 to 24 carbon atoms, such as a phenylthio group, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, Dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 32 carbon atoms, more preferably An arylsulfinyl group having 6 to 24 prime atoms, such as a phenylsulfinyl group, an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as a methylsulfonyl group, ethyl Sulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably having 6 to 48 carbon atoms, more preferably An arylsulfonyl group having 6 to 24 carbon atoms, for example, a phenylsulfonyl group, 1-naphthylsulfonyl group), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, Rufamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphonyl Groups (preferably phosphonyl groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphinoylamino groups (preferably A phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, and examples thereof include a diethoxyphosphinoylamino group and a dioctyloxyphosphinoylamino group.

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

In the general formula (1), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to each other to form 5-membered, 6-membered or 7-membered A ring may be formed. In addition, as a ring formed, there exists a saturated ring or an unsaturated ring. Examples of the 5-membered, 6-membered or 7-membered saturated or unsaturated ring include a pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring and piperidine ring. , Cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring and pyridazine ring, preferably benzene ring and pyridine ring.
In addition, when the formed 5-membered, 6-membered and 7-membered rings are further substitutable groups, they are substituted with any of the monovalent substituents described for R ^{1 to} R ^6. In the case where it is substituted with two or more substituents, these substituents may be the same or different.

In the general formula (1), the R ¹ and R ⁶ are preferably an alkylamino group, an arylamino group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, or a sulfonamide group among the above. An amide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are more preferable, and a carbonamide group and a ureido group are particularly preferable.

In the general formula (1), as R ² and R ⁵ , among the above, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, and a carbamoylsulfonyl group Preferred are alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoyl. A sulfonyl group is more preferable, and an alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.

In the general formula (1), R ³ and R ⁴ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and more preferably A substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group;

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

In general formula (1), when R ³ and R ⁴ represent an aryl group, the aryl group preferably includes a substituted or unsubstituted phenyl group and a substituted or unsubstituted naphthyl group, more preferably A substituted or unsubstituted phenyl group.

In the general formula (1), when R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group is preferably a substituted or unsubstituted 2-thienyl group, a substituted or unsubstituted 4-pyridyl group, A substituted or unsubstituted 3-pyridyl group, a substituted or unsubstituted 2-pyridyl group, a substituted or unsubstituted 1-pyridyl group, a substituted or unsubstituted 2-furyl group, a substituted or unsubstituted 2-pyrimidinyl group, Substituted or unsubstituted 2-benzothiazolyl group, substituted or unsubstituted 1-imidazolyl group, substituted or unsubstituted 1-pyrazolyl group, substituted or unsubstituted benzotriazol-1-yl group, more preferably substituted or unsubstituted Unsubstituted 2-thienyl group, substituted or unsubstituted 4-pyridyl group, substituted or unsubstituted 1-pyridyl group, substituted or unsubstituted Conversion of 2-furyl group, a substituted or unsubstituted 2-pyrimidinyl group.

In the general formula (1), R ⁷ represents a hydrogen atom, a halogen atom, or an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl, Butyl, isopropyl, t-butyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl), an aryl group (preferably having 6 to 24 carbon atoms, more preferably 6 to 12 carbon atoms, Phenyl, naphthyl), or a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl) Represents.

Among the above, R ⁷ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic ring, more preferably a hydrogen atom or an alkyl group, and still more preferably a hydrogen atom.

The alkyl group, aryl group, and heterocyclic group of R ⁷ may be substituted with the substituents described above for R ^{1 to} R ⁶ , for example, and may be substituted with two or more substituents. These substituents may be the same or different.

Next, the metal atom or metal compound in which the compound represented by the general formula (1) coordinates to form a dipyrromethene dye will be described.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or Divalent metal chlorides are included. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl ₃ , InCl ₃ , FeCl ₂ , TiCl ₂ , SnCl ₂ Further, metal chlorides such as SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included. Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is preferable. Most preferred. Among these, Zn is particularly preferable.

Preferred embodiments of the dipyrromethene dye in which the compound represented by the general formula (1) is coordinated to a metal atom or a metal compound are shown below.
That is, in the general formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxy group, cyano group, alkoxy group, Aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group , Sulfonamido group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group,
R ² and R ⁵ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydroxy group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy Group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamido group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group Or a sulfamoyl group,
R ³ and R ⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxy group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy Group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, sulfonamido group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl A group, an arylsulfonyl group, a sulfamoyl group, or a phosphinoylamino group,
R ⁷ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group,
The aspect whose metal atom or metal compound is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO is mentioned.

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

  Among the dipyrromethene dyes in which the compound represented by the general formula (1) is coordinated to a metal atom or a metal compound, the dipyrromethene dye represented by the following general formula (C) is preferable in terms of light resistance and heat resistance. Used for.

In the general formula (C), R ^{2 to} R ⁵ each independently represent a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic ring. Represents a group. Ma represents a metal or a metal compound. X ³ and X ⁴ each independently represent NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, Or represents a sulfur atom. Y ¹ represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), or a nitrogen atom. Y ² represents a nitrogen atom or a carbon atom. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-, 6-, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. When a is 2, X ⁵ may be the same or different. In addition, the dipyrromethene dye represented by the general formula (C) includes a tautomer.

Each substituent of the general formula (C) will be described in detail.
Wherein ^R 2 to R ⁵ have the same meanings as ^R 2 to R ⁵ in the general formula (1), specific examples and preferred substituents are also the same.

When the substituents of R ² and R ⁵ are further substitutable substituents, for example, they may be substituted with the substituents described above for the general formula (1), and may be substituted with two or more substituents. The substituents may be the same or different.

Among the above, R ² and R ⁵ are preferably a cyano group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, or an alkylsulfonyl group, and more preferably an alkoxycarbonyl group or a carbamoyl group. Among the above, R ³ and R ⁴ are preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted group. A phenyl group is more preferred.

R ⁷ has the same meaning as R ⁷ in formula (1), and specific examples and preferred substituents are also the same.

In the general formula (C), Ma represents a metal atom or a metal compound. The metal atom or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or Divalent metal chlorides are included. For example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., and AlCl ₃ , InCl ₃ , FeCl ₂ , TiCl ₂ , SnCl ₂ , SiCl _2, GeCl ₂ metal chlorides, such as, TiO, metal oxides such as VO, include metal hydroxides such as Si _{(OH) 2.} Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is preferable. Most preferred. Among these, Zn is particularly preferable.

In the general formula (C), X ³ and X ⁴ each independently represent NR, an oxygen atom, or a sulfur atom. Here, R is a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms) An alkenyl group, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, for example, phenyl, naphthyl), A heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-thienyl; 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), acyl group (preferably having 1 to 24 carbon atoms, more preferably An acyl group having 2 to 18 carbon atoms, for example, acetyl, pivaloyl, 2-ethylhexyl, benzoyl, cyclohexanoyl), an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably an alkylsulfonyl having 1 to 18 carbon atoms) A group such as methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylsulfonyl, naphthyl) Sulfonyl).

The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group of R may be substituted with the substituents described in R ^{2 to} R ⁵ , for example. In the case where the substituent is substituted, these substituents may be the same or different.

In General Formula (C), Y ¹ represents NRc or a nitrogen atom, Rc has the same meaning as R in X ³ and X ⁴ , and the preferred embodiment is also the same.

In the general formula (C), R ⁸ and R ⁹ are alkyl groups (preferably linear, branched, or cyclic alkyl groups having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, for example, Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl group (preferably having 2 to 24 carbon atoms, more preferably An alkenyl group having 2 to 12 carbon atoms, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, , Phenyl, naphthyl), a heterocyclic group (preferably a C1-C24, more preferably a C1-C12 heterocyclic group, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), an alkoxy group (preferably having 1 to 36 carbon atoms) More preferably an alkoxy group having 1 to 18 carbon atoms, such as methoxy, ethoxy, propyloxy, butoxy, hexyloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy), an aryloxy group (preferably having 6 to 6 carbon atoms). 24, more preferably an aryloxy group having 1 to 18 carbon atoms, for example, phenoxy, naphthyloxy), an alkylamino group (preferably having 1 to 36 carbon atoms, more preferably an alkylamino group having 1 to 18 carbon atoms, For example, methylamino, ethylamino, propylamino, butyl Amino, hexylamino, 2-ethylhexylamino, isopropylamino, t-butylamino, t-octylamino, cyclohexylamino, N, N-diethylamino, N, N-dipropylamino, N, N-dibutylamino, N-methyl -N-ethylamino), an arylamino group (preferably an arylamino group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, such as phenylamino, naphthylamino, N, N-diphenylamino, N- Ethyl-N-phenylamino) or a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms such as 2-aminopyrrole, 3-aminopyrazole, 2 -Aminopyridine, 3-aminopyridine).

Among the above, R ⁸ and R ⁹ are preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms, or 6 to 15 carbon atoms. Of these, a substituted or unsubstituted phenyl group is more preferred.

In the general formula (C), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group represented by R ⁸ and R ⁹ When it is a substitutable group, for example, it may be substituted with the substituent described in R ^{2 to} R ⁵ , and when it is substituted with two or more substituents, those substituents May be the same or different.

In the general formula (C), R ⁸ and Y ¹ are bonded to each other to form a 5-membered ring with a carbon atom (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran, Benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or 7-membered ring (eg, cyclo Heptane, hexamethyleneimine).

In the general formula (C), R ⁹ and Y ² are bonded to each other to form a 5-membered ring with a carbon atom (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole, furan, thiophene, indole, benzofuran, Benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline), or 7-membered ring (eg, cyclo Heptane, hexamethyleneimine).

In the general formula (C), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ⁸ and Y ¹ and R ⁹ and Y ² are substitutable rings, The substituents described above for R ^{2 to} R ⁵ may be substituted, and when substituted with two or more substituents, the substituents may be the same or different.

In the general formula (C), X ⁵ may be any group that can be bonded to Ma. Specifically, water, alcohols (for example, methanol, ethanol, propanol) and the like, The compounds described in “Metal Chelate” ([1] Takeichi Sakaguchi / Keihei Ueno (1995 Nanedo), [2] (1996), [3] (1997), etc.) can be mentioned. Among these, water, carboxylic acid compounds, sulfonic acid compounds, or alcohols are preferable in terms of production, and water, carboxylic acid compounds, or sulfonic acid compounds are more preferable. a represents 0, 1, or 2. When a is 2, X ⁵ may be the same or different.

A preferred embodiment of the compound represented by the general formula ^{(C), and} the R 2 to R ⁵ are each independently a preferred embodiment described in the description of the ^R 2 to R ^5, the ^{R 7} in the ^{R 7} In the preferred embodiment described in the description, Ma is Zn, Cu, Co, or VO, X ³ and X ⁴ are each independently NR (R is a hydrogen atom, an alkyl group) or an oxygen atom, Y ¹ NRc (Rc is a hydrogen atom, an alkyl group) or a nitrogen atom, Y ² is a nitrogen atom or a carbon atom, R ⁸ and R ⁹ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group Or an alkylamino group, X ⁵ is a group bonded through an oxygen atom, and a is 0 or 1. R ⁸ and Y ¹ may be bonded to each other to form a 5- or 6-membered ring, or R ⁹ and Y ² may be bonded to each other to form a 5- or 6-membered ring.

As a more preferable embodiment of the compound represented by the general formula (C), R ² and R ⁵ are each independently an alkoxycarbonyl group or a carbamoyl group, and R ³ and R ⁴ are each independently substituted or unsubstituted. An alkyl group or a substituted or unsubstituted phenyl group, R ⁷ is a hydrogen atom or a methyl group, and R ⁸ and R ⁹ are each independently a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group. , X ³ and X ⁴ are oxygen atoms, Y ¹ is NRc (Rc is a hydrogen atom or an alkyl group) or a nitrogen atom, Y ² is a nitrogen atom, Ma is Zn, and X ⁵ is a carboxylic acid A compound or a sulfonic acid compound.

In the general formula (C), the site into which a polymerizable group for multimerization (formation of a dye multimer) is introduced is not particularly limited, but in terms of synthesis compatibility, R ^{2 to} R ⁵ , It is preferably introduced into any one or more of R ⁸ , R ⁹ and X ⁵ , and more preferably, any one or more of R ³ , R ⁴ , R ⁸ and R ⁹ More preferably R ⁸ and / or R ⁹ .

The molar extinction coefficient of the dipyrromethene dye represented by the general formula (C) is preferably as high as possible from the viewpoint of film thickness. The maximum absorption wavelength λmax is preferably 520 nm to 580 nm, more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. The maximum absorption wavelength and molar extinction coefficient are measured with a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).
The melting point of the dipyrromethene dye represented by the general formula (C) should not be too high from the viewpoint of solubility.

(1-2) Azo dye -Magenta dye-
An azo dye represented by the following general formula (D) is preferably used as a magenta dye used for a color resist for red or inkjet ink.

In the general formula (D), R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Represents an alkylsulfonyl group or an arylsulfonyl group, A represents an aryl group or an aromatic heterocyclic group, and Z ^{1 to} Z ³ each independently represent —C (R ⁵ ) ═ or —N═. R ⁵ represents a hydrogen atom or a substituent.

Each substituent of the general formula (D) will be described in detail.
In general formula (D), R ^{1 to} R ⁴ are each independently a hydrogen atom or an alkyl group (preferably a straight chain, branched chain, or cyclic group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms). An alkyl group of, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), an alkenyl group (preferably having a carbon number) An alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, such as vinyl, allyl, 3-buten-1-yl), an aryl group (preferably 6 to 36 carbon atoms, more preferably 6 to 6 carbon atoms). 18 aryl groups such as phenyl and naphthyl, and heterocyclic groups (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms). A terocyclic group such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), acyl group ( Preferably it is a C1-C24 acyl group, More preferably, it is a C2-C18 acyl group, for example, acetyl, pivaloyl, 2-ethylhexyl, benzoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably C1-C10, More preferably, it is a C1-C6 alkoxycarbonyl group, for example, methoxycarbonyl, ethoxycarbonyl), an aryloxycarbonyl group (preferably a C6-C15, more preferably a C6-C10 aryloxycarbonyl group). , Eg phenoxycarbonyl), carbamoyl group (preferred Is a carbamoyl group having 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, such as dimethylcarbamoyl), an alkylsulfonyl group (preferably having 1 to 24 carbon atoms, and more preferably having 1 to 18 carbon atoms). And, for example, methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl) or arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms such as phenylsulfonyl, naphthyl) Sulfonyl).

R ¹ and R ³ are preferably each independently an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R ² and R ⁴ are preferably each independently a hydrogen atom or an alkyl group.
When R ^{1 to} R ⁴ are substitutable groups, for example, they may be substituted with the substituents described in R ^{1 to} R ⁶ of the general formula (1), and two or more substituents In the case of having these, the substituents may be the same or different.

R ¹ and R ² , R ¹ and R ⁵ (when Z ¹ or Z ² is —C (R ⁵ ) =), R ³ and R ⁴ , R ³ and R ⁵ (Z ¹ is —C (R ⁵ )) May be bonded to each other to form a 5-membered or 6-membered ring.

Z ^{1 to} Z ³ each independently represent —C (R ⁵ ) ═ or —N═, and R ⁵ represents a hydrogen atom or a substituent. The substituent for R ^5, for example, the substituent described in the explanation of ^R 1 to R ⁶ in the general formula (1). When the substituent of R ⁵ is a further substitutable group, for example, it may be substituted with the substituent described in R ^{1 to} R ⁶ of the general formula (1), and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.

The Z ¹ to Z ^3, preferably, ^{Z 1} is a -N =, ^{Z 2} is -C a ^(R 5) = or a -N =, ^{Z 3} is -C ^(R 5) = at is there. More preferably, a ^{Z 1} is -N =, ^{Z 2} and ^{Z 3} -C ^(R 5) is =.

A represents an aryl group or an aromatic heterocyclic group. The aryl group of A and the aromatic heterocyclic group may further have, for example, the substituents described in R ^{1 to} R ⁶ of the general formula (1), and may be two or more substituents. When substituted, these substituents may be the same or different.
A is preferably an aromatic heterocyclic group. More preferably, imidazole ring, pyrazole ring, triazole ring, thiazole ring, oxazole ring, 1,2,4-thiadiazole ring, 1,3,4-thiadiazole ring, pyridine ring, pyrimidine ring, pyrazine ring, benzopyrazole ring, Examples include a benzothiazole ring.

In the general formula (D), the site into which a polymerizable group for multimerization (formation of a dye multimer) is introduced is not particularly limited, but in terms of synthesis compatibility, R ¹ , R ² and It is preferably introduced into any one or more of A, and more preferably R ¹ and / or A.

  The azo dye represented by the general formula (D) is more preferably represented by the general formula (D ′).

In the general formula (D ′), R ^{1 to} R ⁴ have the same meanings as those in the general formula (D), and preferred ranges thereof are also the same. Ra represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.2 or more, and Rb represents a hydrogen atom or a substituent. Rc represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group.
The Rb substituents, e.g., substituents described in ^R 1 to R ⁶ in the general formula (1).

  An azo dye represented by the following general formula (E) is also preferably used as the magenta dye used in the color resist for red and inkjet ink.

In the general formula (E), R ^{11 to} R ¹⁶ each independently represents 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.

Each substituent of the general formula (E) will be described in detail.
R ^{11 to} R ¹⁶ each independently represents 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 (here, a saturated aliphatic group including a cycloalkyl group or a bicycloalkyl group), or an alkenyl group having 2 to 30 carbon atoms. (Here, it means an unsaturated aliphatic group having a double bond including a cycloalkenyl group and a bicycloalkenyl group.), An alkynyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 carbon atoms. -30 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, 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 (an alkylamino group, an anilino group, 2) 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 aryloxy group having 7 to 30 carbon atoms. Carbonylamino 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, C1-C30 alkyl or arylsulfinyl group, C1-C30 alkyl or arylsulfonyl group, C2-C30 acyl group, C6-C30 aryloxycarbonyl group, C2-C30 aliphatic oxycarbonyl group, C1-C30 carbamoyl group, C3-C30 Reel or heterocyclic-azo group, and imide group, each group may further have a substituent.

R ¹¹ and R ¹² are preferably each independently a hydrogen atom, a heterocyclic group, or a cyano group, and more preferably a cyano group.
R ¹³ and R ¹⁴ are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and more preferably a substituted or unsubstituted alkyl group.
R ¹⁵ and R ¹⁶ are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and more preferably a substituted or unsubstituted alkyl group.

In the general formula (E), there are no particular limitations on the site where a polymerizable group for multimerization (formation of a dye multimer) is introduced, but in terms of synthesis compatibility, R ¹³ , R ¹⁵ , and It is preferably introduced into any one or more of R ¹⁶ , more preferably R ¹³ and / or R ¹⁵ , and still more preferably R ¹³ .

-Yellow dye-
As yellow dyes used in red and green color resists and inkjet inks, azo dyes represented by the following general formulas (F), (G) and (I) are suitable (including tautomers thereof). ).

In the general formula (F), R ³⁰ represents a hydrogen atom or a substituent, and R ³¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Represents a group. X ³⁰ represents an —OM group, —N (R ³² ) (R ³³ ), M represents a hydrogen atom, an alkyl group, or a metal atom or an organic base pair necessary for neutralizing a charge, and R ³² and R ³³ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. A ³⁰ represents an aryl group or an aromatic heterocyclic group.

Each substituent of the general formula (F) will be described in detail.
R ³⁰ represents a hydrogen atom or a substituent. Examples of the substituent include the substituents described in the R ¹ to R ⁶ in the general formula (1). Among these, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group is preferable, and a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group is more preferable.

R ³¹ is a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms) And, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, for example, phenyl or naphthyl), a heterocyclic ring A group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-thienyl, 4 -Pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), acyl group (preferably having 1 to 24 carbon atoms, more preferably carbon An acyl group having 2 to 18, for example, acetyl, pivaloyl, 2-ethylhexyl, benzoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 1 to 6 carbon atoms, more preferably having 1 to 4 carbon atoms) And represents a carbamoyl group (preferably a carbamoyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, for example, N, N-dimethylcarbamoyl).

A ³⁰ is synonymous with A in the general formula (D), and the preferred embodiment is also the same.

In the general formula (F), the site into which a polymerizable group for multimerization (formation of a dye multimer) is introduced is not particularly limited, but R ³¹ and / or A ^{30 in} terms of synthesis compatibility. Is preferred.

In the general formula (G), R ³⁴ represents a hydrogen atom or a substituent, and R ³⁵ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Represents. Z ³⁰ and Z ³¹ each independently represent —C (R ³⁶ ) ═ or —N═, and R ³⁶ represents a hydrogen atom or a substituent. A ³¹ represents an aryl group or an aromatic heterocyclic group.

Each substituent of the general formula (G) will be described in detail.
R ³⁴ represents a hydrogen atom or a substituent, and has the same meaning as R ³⁰ in the general formula (F), and preferred embodiments thereof are also the same.

R ³⁵ represents a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl , Butyl, isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably alkenyl having 2 to 12 carbon atoms) A group such as vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms such as phenyl or naphthyl), hetero A cyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), acyl group (preferably having 1 to 24 carbon atoms, more preferably An acyl group having 2 to 18 carbon atoms, for example, acetyl, pivaloyl, 2-ethylhexyl, benzoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms) Group, for example, a methoxycarbonyl group, an ethoxycarbonyl group) or a carbamoyl group (preferably a carbamoyl group having 1 to 10 carbon atoms, more preferably a carbamoyl group having 1 to 6 carbon atoms, for example, N, N-dimethylcarbamoyl). .

Z ³⁰ and Z ³¹ each independently represent —C (R ³⁶ ) ═ or —N═, and R ³⁶ represents a hydrogen atom or a substituent. Examples of the substituent of R ^36, for example, the substituent described in the explanation of ^R 1 to R ⁶ in the general formula (1). When the substituent of R ³⁶ is a further substitutable group, for example, it may be substituted with the substituent described in R ^{1 to} R ⁶ of the general formula (1), and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.
As Z ³⁰ and Z ³¹ , Z ³⁰ is preferably —N═ and Z ³¹ is —C (R ³⁶ ) ═.

A ³¹ is synonymous with A in the general formula (D), and preferred embodiments thereof are also the same.

In the general formula (G), there are no particular restrictions on the site where a polymerizable group for multimerization (formation of a dye multimer) is introduced, but R ³⁴ and / or A ^{31 is preferred} in terms of synthesis compatibility. Is preferred.

In the general formula (I), R ⁴² represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom or a substituent, A ³³ represents an aryl group or an aromatic heterocyclic group.

Each substituent of the general formula (I) will be described in detail.
^R42 represents a hydrogen atom or an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl. , Isobutyl, t-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), an alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms) , For example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably an aryl group having 6 to 36 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, such as phenyl or naphthyl), or a heterocyclic ring A group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl).

R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom or a substituent, and examples of the substituent include the substituents described in R ^{1 to} R ⁶ of the general formula (1). When the substituents of R ⁴³ and R ⁴⁴ are further substitutable groups, for example, they may be substituted with the substituents described in R ^{1 to} R ⁶ of the general formula (1), and two or more In the case where the substituent is substituted, these substituents may be the same or different.

A ³³ is synonymous with A in the general formula (D), and the preferred embodiment is also the same.

In the general formula (I), there is no particular limitation on the site where a polymerizable group for multimerization (formation of a dye multimer) is introduced. However, R ⁴² and / or A ^{33 is preferred} in terms of synthesis compatibility. Is preferred.

  Among the above azo dyes, the yellow dye is preferably an azo dye represented by the general formula (I) from the viewpoint of spectroscopy, and represented by the general formula (F) from the viewpoint of light resistance and heat resistance. Azo dyes are preferred.

Azo dyes or dipyrromethene dyes are disclosed in JP-A-2005-189802, JP-A-2007-250224, JP-A-2006-124634, JP-A-2007-147784, JP-A-2007-277176. , JP 2008-292970 A, US Pat. No. 5,789,560 and the like.
Also, known methods can be applied to the method of multimerizing the dye and the method of introducing a polymerizable group into the dye. Specific examples are given in the examples.

(2) Constituent Unit Having Group Derived from Dye The constituent unit having a group derived from the dye is preferably a constituent unit having a group derived from the preferred dye group. Although the specific example of the structural unit which has group derived from a pigment | dye below is shown, this invention is not limited to the following. Hereinafter, a structural unit having a group derived from a dye may be referred to as a “dye unit”.

  In the example of the dye unit, in the case of a dye unit containing two or more carboxyl groups, a tautomer dye unit by an isomerization reaction occurring between these carboxyl groups and a metal atom (zinc, copper, cobalt, etc.) Is also shown at the same time. Among the dye unit examples described above, 1-1, 1-3, 1-4, 1-6, 2-4, 2-5, 2-6, 2-7, 2-9, 2-10, 2 -11, 2-12, 2-14, 2-17, 2-18, 2-19, 2-20, and 2-23, and specific examples thereof include dye unit example 2-7 shown below. -7 and 2-7 ′ below are represented simultaneously.

  In addition, the following specific examples are given as examples of the dye unit.

(3) Structural Unit Having Polymerizable Group Examples of the structural unit having a polymerizable group contained in the polymerizable group-containing dye multimer include the following structural units.
That is, a polymerizable compound having a group that reacts with the structural unit (for example, methacrylic acid, acrylic acid, hydroxyethyl methacrylate, etc.) derived from a copolymerized component copolymerized with the above-described dye compound (for example, , Glycidyl methacrylate, methacryloxyethyl isocyanate, and the like).
When the dye compound has a reactive group, it is derived from the structural unit having a polymerizable group and the dye by reacting the polymerizable compound having a group that reacts with the structural unit having a group derived from the dye. It is good also as a structural unit which served as the structural unit which has the group to do.
In the dye compound, a polymerizable group different from the polymerizable group for multimerization of the dye compound is introduced into the azo dye skeleton or the dipyrromethene dye skeleton, and the dye compound is polymerized to be polymerized. It may be a structural unit having a sex group.
Furthermore, after polymerizing a dye compound or a copolymer component that does not have a dye skeleton in which a group that becomes a precursor of a polymerizable group is introduced, various reactions (for example, treatment with an alkaline solution) are performed to obtain a polymerizable group. A structural unit having a polymerizable group can be formed by generating a polymerizable group from a group that becomes a precursor of the above.

  The polymerizable group contained in the structural unit having the polymerizable group (hereinafter sometimes referred to as “polymerizable unit”) is not particularly limited, and includes, for example, an ethylenically unsaturated group (for example, methacryl group, acrylic group). , Styryl groups, etc.), cyclic ether groups (for example, epoxy groups, oxetanyl groups, etc.). Among these, an ethylenically unsaturated group is preferable in terms of heat resistance and solvent resistance.

  Specific examples of the structural unit having a polymerizable group include the following. However, the present invention is not limited to these.

(4) Other constitutional units The polymerizable group-containing dye multimer may contain other copolymerization components as constitutional units as long as the effects of the present invention are not impaired. When the polymerizable group-containing dye multimer is synthesized by radical polymerization, the copolymer component may be any monomer having at least one ethylene group, and specific examples thereof include the following.
Examples of the copolymerizable monomer include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid, α-hydroxymethylacrylic acid, etc.), and salts derived from the acrylic acid, Esters or amides (for example, sodium acrylate, tetramethylammonium methacrylate, sodium 2-acrylamido-2-methylpropanesulfonate, sodium 3-acryloyloxypropanesulfonate, acrylamide, methacrylamide, diacetone acrylamide, methyl acrylate , Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-dimethylaminoethyl Tacrylate, benzyl methacrylate, etc.), vinyl esters (eg, vinyl acetate, etc.), acrylonitrile, aromatic vinyl compounds (eg, styrene, p-styrene carboxylic acid, p-styrene sulfonic acid, etc.), vinylidene chloride, vinyl alkyl ether ( For example, vinyl ethyl ether), maleic acid ester, itaconic acid, vinyl imidazole, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole and the like.
Specific examples of the structural unit when the copolymerizable monomer is polymerized are shown below, but the present invention is not limited thereto.

  When the polymerizable group-containing dye multimer is synthesized by polycondensation or polyaddition (for example, polyester, polyurea, polyamide, polyamic acid, etc.), the copolymerizable monomer includes at least two reactive groups. (Eg, alcohols (eg, 1,6-hexanediol, 2,2-bishydroxymethylpropanoic acid, etc.), isocyanates (eg, 1,3-tolyl diisocyanate, 1,6-hexane diisocyanate, etc.), amines (eg, , Ethylenediamine, trimethylenediamine, etc.), acid anhydrides, etc.).

As the copolymerizable monomer, a monomer having an alkali-soluble group is preferable from the viewpoint of improving the color pattern forming property. For example, methacrylic acid, acrylic acid, and the like are preferable.
The polymerizable group-containing dye multimer preferably contains 1 to 40% by mass, and preferably 3 to 20% by mass of an alkali-soluble group from the viewpoint of color pattern formation when applied to a colored curable composition. Is more preferable, and it is still more preferable to contain 5-15 mass%.
Hereinafter, in the polymerizable group-containing dye multimer, a structural unit derived from a monomer having an alkali-soluble group may be referred to as an “alkali-soluble unit”.

(5) Specific examples of polymerizable group-containing dye multimer In the polymerizable group-containing dye multimer of the present invention, the type of the dye unit, the polymerizable unit, and other constituent units (preferably the alkali-soluble unit). The combination and the content (% by mass) of each unit are not particularly limited.

  As a preferred embodiment of the above combination, the dye unit is a structural unit having a group derived from the aforementioned preferred dye group, and more preferably has a group derived from the dipyrromethene dye represented by the general formula (C). A structural unit or a structural unit having a group derived from an azo dye represented by formula (E), the polymerizable unit is a structural unit having an ethylenically unsaturated group, and the alkali-soluble unit is: It is a structural unit derived from methacrylic acid or acrylic acid.

Tables 1 and 2 below show specific compound examples of the polymerizable group-containing dye multimer of the present invention, but the present invention is not limited thereto.
In Table 1 and Table 2 below, the number of each unit corresponds to the number of the exemplified compound described above, and the dye unit (4-1) is a compound represented by the following structural formula.

  The content of the polymerizable group-containing dye multimer in the colored curable composition of the present invention varies depending on the molecular weight and the molar extinction coefficient, but is 0.5 to 80% by mass with respect to the total solid components of the composition. Is preferable, 0.5 to 70 mass% is more preferable, and 1 to 70 mass% is particularly preferable.

In the colored curable composition of the present invention, the polymerizable group-containing dye multimer 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, A dye or a pigment may be sufficient and the well-known pigment | dye conventionally used for 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, Xanthene, phthalocyanine, benzopyran, and indigo dyes can be used.

(B) Polymerizable compound The polymerizable compound is polymerized or cross-linked, for example, by exposure to UV light of 400 nm or less or heat to insolubilize the colored curable composition in an alkaline developer. Distinguish between exposed parts and enable pattern formation.
Moreover, when applying the colored curable composition of this invention to the inkjet method, the cured colored pixel can be obtained by containing a polymeric compound.

  Specifically, the polymerizable compound is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any of chemical forms such as monomers, prepolymers (ie, dimers or trimers), oligomers, and mixtures thereof, and (co) polymers thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

Examples of monomers and their (co) polymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and their (co) It is a polymer. In addition, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxy group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in JP-A-2009-288705, paragraphs 0095 to 0108 can also be suitably used in the present invention.

The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group as a polymerizable monomer and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso Polyfunctional alcohols such as nurate, glycerin and trimethylolethane added with ethylene oxide or propylene oxide and then (meth) acrylated, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane acrylates as described in JP-B-37193, polyester acrylates described in JP-B-48-64183, JP-B-49-43191, JP-B-52-30490, epoxy Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates and the like, which are reaction products of a resin and (meth) acrylic acid, and mixtures thereof.
Among the above, an acrylic compound having 3 or more acryloyl groups in the molecule is particularly preferable.

  Further, examples of the compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group include paragraphs 0254 to 0257 and JP-A-2009-29 in JP-A-2008-292970. The compounds described in paragraphs 0054 to 0068 of No. 13206 are also suitable examples.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used.

  In the general formulas (MO-1) to (MO-5), R, T, and Z each represent the following substituent or linking group, and n represents an integer of 0 to 14. In the following R, T, and Z, m represents an integer of 1-8. A plurality of R and T present in one molecule may be the same or different. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

  As specific examples of the radical polymerizable monomers represented by the general formulas (MO-1) to (MO-5), the compounds described in paragraphs 0248 to 0251 of JP-A-2007-26979 are used in the present invention. Can also be suitably used.

The content of the polymerizable compound in the colored curable composition of the present invention is preferably 0.1 to 90% by mass, more preferably 1.0 to 80% by mass, based on the solid content in the colored curable composition. 2.0-70 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.

  The content ratio (A: B) (mass%) of (A) polymerizable group-containing dye multimer and (B) polymerizable compound in the colored curable composition of the present invention is 1: 0 from the viewpoint of pattern formation. 1 to 1:10 is preferable, and 1: 0.5 to 1: 5 is more preferable.

(C) Polymerization initiator The colored curable composition of the present invention preferably contains at least one kind of a polymerization initiator that generates radicals and acids in order to further increase the speed of the curing reaction. When forming, it becomes essential. 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.

  The colored curable composition of the present invention preferably contains a photopolymerization initiator as a polymerization 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 at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron complex and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs 0070 to 0077 of JP-A No. 2004-295116. Among these, an oxime compound is preferable from the viewpoint of rapid polymerization reaction.

The oxime-based compound (hereinafter also referred to as “oxime-based photopolymerization initiator”) is not particularly limited. For example, JP-A-2000-80068, WO02 / 100903A1, JP-A-2001-233842, etc. The described oxime compounds are mentioned.
Specific examples include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (o-benzoyloxime) -1- [4- (phenylthio). Phenyl] -1,2-pentanedione, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (o-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (o-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (o-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (o-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (o-acetyloxime) -1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (o-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (o-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (o-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (o-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) Such as 9H- carbazol-3-yl] ethanone and the like. However, it is not limited to these.

  Among these, 2- (o-benzoyloxime) -1- [4- (phenylthio) is obtained in that a good pattern (particularly, the rectangularity of the pattern in the case of a solid-state imaging device) can be obtained with a smaller exposure amount. Oxime-o such as phenyl] -1,2-octanedione, 1- (o-acetyloxime) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone -Acyl compounds are particularly preferred, and specific examples include CGI-124 and CGI-242 (above, manufactured by BASF Japan).

  Moreover, in this invention, the compound represented by following formula (1) or formula (2) is more preferable as an oxime type compound from a viewpoint of a sensitivity, temporal stability, and the coloring at the time of post-heating.

  In the above formulas (1) and (2), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.

  R is preferably an acyl group from the viewpoint of increasing sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.

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

  Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

X may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Alkenyl group, optionally substituted alkynyl group, optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted alkylthioxy group, substituted An arylthio group which may have a group and an amino group which may have a substituent are preferable.
Moreover, n in Formula (1) and Formula (2) is preferably an integer of 1 to 2.

  Hereinafter, although the specific example of a compound represented by Formula (1) or Formula (2) is shown below, this invention is not limited to these.

  In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph 0079 of JP-A No. 2004-295116 may be used in the colored curable composition of the present invention. .

  The content of the photopolymerization initiator in the colored curable composition is preferably 0.01 to 50% by mass, more preferably 1 to 30% by mass, and 1 to 20% by mass with respect to the solid content of the polymerizable compound. Particularly preferred. When the content is within the above range, the polymerization proceeds well and good film strength can be obtained. A photoinitiator can be contained individually by 1 type or in combination of 2 or more types.

(D) Solvent When preparing the colored curable composition of the present invention, a solvent is preferably used. 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.
It is also preferable to mix two or more kinds of these organic solvents from the viewpoints of solubility of the ultraviolet absorber and the alkali-soluble resin, improvement of the coated surface, and the like. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The amount of the solvent in the colored curable composition of the present invention is not particularly limited, but is preferably 20 to 95% by mass, and preferably 40 to 90% by mass from the viewpoint of ensuring the stability and applicability of the colored curable composition. Is more preferable, and 60-85 mass% is still more preferable.

(Other ingredients)
[binder]
The colored curable composition preferably contains a binder. 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 a linear organic polymer include the polymers described in paragraphs 0227 to 0234 of JP-A-2008-292970.

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

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

  As the alkali-soluble binder, it is also preferable to use a polymer (a) obtained by polymerizing a compound represented by the following formula (3) (hereinafter sometimes referred to as “ether dimer”).

In the formula (3), R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

When the colored curable composition of this invention contains the said polymer (a), the heat resistance and transparency of the cured coating film formed using this composition improve more.
In the formula (3) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited. Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl group, 2-ethylhexyl group, etc., linear or branched An aryl group such as a phenyl group; a cyclohexyl group, a t-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isobornyl group, an adamantyl group, a 2-methyl-2-adamantyl group, etc. An alicyclic group; an alkyl group substituted with alkoxy such as 1-methoxyethyl group, 1-ethoxyethyl group, etc .; an alkyl substituted with aryl group such as benzyl group; Group; and the like.
Among these, a group containing a primary or secondary carbon that is difficult to be removed by an acid or heat, such as a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group, is particularly preferable in terms of heat resistance.
Note that R ¹ and R ² may be the same type of substituent or different substituents.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds.

The alkali-soluble binder is also preferably a polymer having an epoxy group.
In order to introduce an epoxy group into an alkali-soluble binder, for example, a monomer having an epoxy group (hereinafter sometimes referred to as “monomer for introducing an epoxy group”) is polymerized as a monomer component. Good. Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types. When the monomer component in obtaining the alkali-soluble binder also includes a monomer for introducing the epoxy group, the content ratio is not particularly limited, but is 5 to 70% by mass in the total monomer component, Preferably it is 10-60 mass%.

The alkali-soluble binder is also preferably a polymer having an acid group.
The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more. In order to introduce an acid group into an alkali-soluble binder, for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter sometimes referred to as “monomer for introducing an acid group”) .) May be polymerized as a monomer component.
In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.
Examples of the monomer having an acid group include a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid, a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide, maleic anhydride, and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types.
In the case of using a monomer capable of imparting an acid group after polymerization, the treatment for imparting the acid group after polymerization includes a treatment of modifying a part of the polar group of the polymer side chain by a polymer reaction.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a commercially available KS resist 106 ( Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (Daicel Chemical Industries, Ltd.) are preferred.

  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 cross-linking agent to the colored curable composition. The cross-linking agent is not particularly limited as long as the film can be cured by a cross-linking reaction. For example, paragraphs 0237 to 0253 of JP-A-2008-292970. The crosslinking agent as described in above.
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 cure and elution of the unexposed area, and prevent the degree of cure of the exposed area from being insufficient or significantly reducing the elution of the unexposed area. be able to.

[Surfactant]
Various surfactants may be added to the colored curable composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, the colored curable composition of the present invention contains a fluorosurfactant, so that the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness is uniform. And the liquid-saving property can be further improved.
That is, when a film is formed using a coating liquid to which a colored curable composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a colored curable composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), Solsperse 20000 (Japan Rouble) Zole Co., Ltd.).

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, etc. It is.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.

Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the colored curable composition. .

[Polymerization inhibitor]
In the colored curable composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored curable composition. .
Examples of the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- t-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the whole composition.

[Various additives]
In the colored curable composition of the present invention, various additives such as a filler, a polymer compound other than the above, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, etc. may be blended as necessary. I can do it. Examples of these include 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 may be combined at once, or may be combined sequentially 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.

<Color filter and manufacturing method thereof>
The color filter of the present invention is produced using the colored curable composition of the present invention.
The colored curable composition of the present invention can be suitably used for forming colored pixels of color filters used in liquid crystal display devices, organic EL display devices, and solid-state imaging devices (for example, CCD, CMOS, 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. 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.

  The method for producing a color filter by the inkjet method using the colored curable composition of the present invention is not particularly limited, and for example, the method described in paragraphs 0114 to 0128 of JP-A-2008-250188 can be used. .

  Examples of the support used in the method for producing a color filter of the present invention include soda glass, borosilicate glass (pyrex (registered trademark) glass), quartz glass, and quartz glass used for liquid crystal display elements and the like, and a transparent conductive film thereon. Examples include a deposited substrate and a photoelectric conversion element substrate used for an imaging element, such as a silicon substrate and a complementary metal oxide semiconductor (CMOS) substrate. These substrates may have black stripes that separate pixels. Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.

-Pattern formation method using colored curable composition-
A method of forming a color filter by a photolithography method using the colored curable composition of the present invention includes a colored layer forming step of forming a colored layer by applying the colored curable composition on a support, and the colored layer. A pattern-like exposure through a mask to form a latent image, and a development step of developing the colored layer on which the latent image is formed to form a pattern (these steps are included). In addition, it may be referred to as a pattern forming step.) For example, the method described in paragraphs 0277 to 0284 of JP-A-2008-292970 can be mentioned in detail.

[Post-curing process]
In the present invention, it is preferable to carry out a post-curing step of further curing the formed pattern after the development processing in the pattern forming step.
The post-curing step is performed by heating and / or exposure (ultraviolet irradiation), but the formed pattern is further cured to prevent dissolution of the pattern in the step of forming a colored layer in the next color pattern forming step. In addition, the solvent resistance of the pixel of the obtained color filter can be improved.

The post-curing step is preferably an ultraviolet irradiation step by ultraviolet irradiation. Ultraviolet irradiation process, the pattern after performing a developing process in the pattern forming step, for example, ultraviolet exposure [mJ / cm ^2] of 10 times or more of the irradiation light amount of exposure before development [mJ / cm ^2] Irradiate light (UV light). By irradiating the developed pattern with UV light for a predetermined time between the development processing and the heat treatment described later, it is possible to effectively prevent color transfer when heated later. It is preferable that the amount of irradiation light in this step is 10 times or more because color migration between colored pixels and between upper and lower layers can be effectively prevented. Especially, the irradiation light quantity of UV light is preferably 12 times or more and 200 times or less, and more preferably 15 times or more and 100 times or less the exposure amount of the exposure step for forming a pattern.

  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 post-exposure is preferably performed 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 pixels of a plurality of hues, a color filter configured in a desired number of hues by repeating the pattern formation step (and post-curing step if necessary) according to the desired number of colors. Can be produced.

  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.

<Use of the color filter of the present invention>
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. Also, for solid-state image sensors such as CCD image sensors and CMOS image sensors used in digital cameras, digital video cameras, endoscopes, mobile phones, etc., especially high resolution CCD elements and CMOS elements exceeding 1 million pixels. It can be suitably used as a color filter.

Specifically, for example, an alignment film is formed on the inner surface side of the color filter, is opposed to the electrode substrate, and a liquid crystal is filled in the gap portion and sealed, whereby the panel which is the liquid crystal display element of the present invention is obtained. For example, the solid-state image sensor of this invention is obtained by forming a color filter on a light receiving element.
More specifically, the configuration of the solid-state imaging device of the present invention has, for example, a transfer electrode made of a photodiode and polysilicon constituting a light receiving area on a support, and a color filter layer is provided. The structure which laminates | stacks a micro lens is mentioned. 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 and the color resist of the present invention, the color filter and the manufacturing method thereof, and the solid-state imaging device and the image display device including the color filter have been described in detail with various embodiments. It goes without saying that the present invention is not limited to the above embodiment, and 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 “% by 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 109>
An exemplary compound 109 of a polymerizable group-containing dye multimer was synthesized by the method described below.
First, the dye monomer 2-4-A was synthesized by the following method according to the following synthesis scheme.

<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 while maintaining the internal temperature at 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-4,5-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 Dye Monomer 2-4-A>
In a 300 mL three-necked flask, 14.2 g (0.04 mol) of intermediate (d), 6.7 g (0.044 mol) of 4-vinylbenzyl chloride, 16.6 g (0.12 mol) of potassium carbonate, iodide 18 g (0.12 mol) of sodium, 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 the dye monomer 2-4-A. Yield 16.1 g (85% yield). Mass spectral result: (m / z) = 473 ([M + 1] ⁺ , 100%). The absorption maximum wavelength in the absorption spectrum of 2-4-A in ethyl acetate was 496.4 nm.
FIG. 1 shows a solution transmission spectrum of the dye monomer 2-4-A in ethyl acetate.

  Then, according to the following synthesis scheme, 2-4-A and methacrylic acid were copolymerized by the following method.

  In a 100 mL three-necked flask, 14.0 g (0.03 mol) of 2-4-A and 6.0 g (0.07 mol) of methacrylic acid are added, dissolved in propylene glycol methyl ether acetate (60 g), and nitrogen is allowed to flow. The mixture was heated to 75 ° C. 0.69 g of a polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the approximate solution, and the mixture was heated and stirred for 2 hours. Further, 0.69 g of a polymerization initiator was added and stirred for 2 hours, and then the temperature was raised to 90 ° C. and stirred for 2 hours. When the remaining amount of the dye monomer and methacrylic acid in the general solution was confirmed by high performance liquid chromatography, both were 1% by mass or less. Next, p-methoxyphenol (100 mg), dimethyldodecylamine (0.4 g), and glycidyl methacrylate (4.2 g, 0.03 mol) were added to the reaction solution, the temperature was raised to 95 ° C., and the mixture was stirred under air for 10 hours. Then, a 30% by mass propylene glycol methyl ether acetate solution of the polymerizable group-containing dye multimer (Exemplary Compound 109) was synthesized. When the remaining amount of glycidyl methacrylate in the general solution was confirmed by high performance liquid chromatography, it was 1% by mass or less. The obtained dye multimer had a weight average molecular weight (Mw) of 18,000 and an acid value of 90 mgKOH / g.

  Other compounds shown in Table 1 (such as 101) other than those described above can also be synthesized by a method according to the above synthesis examples from a chemical standpoint. In addition, exemplary compounds 105 and 111 in Table 1 are prepared by reacting a diol-containing dye and a carboxylic acid compound with diisocyanate or bisanhydride to synthesize polyurethane or polyester, and then adding glycidyl methacrylate in the same manner as described above. Can be easily synthesized.

[Synthesis Example 2]
<Synthesis of Exemplary Compound 114>
An exemplary compound 114 of a polymerizable group-containing dye multimer was synthesized by the method described below.
First, the dye monomer J-1 was synthesized by the following method according to the following synthesis scheme.

<Synthesis of Compound 7>
206.4 g of isopropyl methyl ketone was stirred in 1 L of methanol, 7 ml of hydrobromic acid (47-49% aqueous solution) was added, and bromine was added dropwise at 30-34 ° C. over 3 hours. Then, it stirred at 30 degreeC for 30 minutes. After neutralization with an aqueous solution in which 124 g of sodium hydrogen carbonate was dissolved in 1.3 L of water, an aqueous solution in which 400 g of sodium chloride was dissolved in 1.3 L of water was added, and the separated liquid reaction product was fractionated.
Separately, 222 g of potassium phthalimide was stirred in 800 ml of dimethylacetamide (DMAc), and the reaction product previously separated by water cooling was added dropwise and stirred at room temperature for 4 hours. Thereafter, 720 ml of water was added by water cooling, and the precipitated crystals were separated by filtration. The obtained crystals were suspended in 1.5 L of toluene, insoluble matters were filtered off, and the filtrate was concentrated to obtain compound 7 (100 g).
Compound 7: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 1.21-1.23 (6H, d), 2.74-2.79 (1H, m), 4.56 (2H, s ), 7.72-7.74 (2H, d), 7.85-7.87 (2H, d).

<Synthesis of Compound 8>
Compound 8 was synthesized by the method described in paragraph 0134 of JP-A-2008-292970.

<Synthesis of Compound 9>
Compound 8 (293 g) and Compound 7 (231 g) were stirred in 1.4 L of methanol under a nitrogen atmosphere, and sodium hydroxide (88 g) was dissolved in 400 ml of water and added dropwise at room temperature. Thereafter, the mixture was refluxed for 8 hours. Thereafter, the mixture was allowed to cool to room temperature, and the precipitated crystals were collected by filtration and washed with 100 ml of methanol to obtain Compound 9 (299 g).
Compound 9: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.88-0.95 (18H, s), 1.00-1.03 (3H, d), 1.17-1.19 (6H, d), 1.20-1.66 (7H, m), 3.38-3.43 (1H, m), 5.19-5.24 (2H, br), 5.95 (1H Br), 6.00 (1H, s), 7.39-7.45 (1H, br).

<Synthesis of Compound 10>
Compound 9 (80 g) was stirred in 250 ml of DMAc at room temperature, 29.2 g of 2-chloropropionyl chloride was added dropwise, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into 500 ml of ethyl acetate and 1 L of water, washed with 500 ml each of saturated sodium bicarbonate water, water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure to obtain Compound 10 (89.4 g).
Compound 10: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.9 (18H, s), 0.96-1.01 (3H, d), 1.20-1.23 (2H, d ), 1.26-1.38 (1H, q), 1.53-1.68 (6H, m), 1.8-1.82 (3H, d), 3.44-3.53 (1H) M) 4.5-4.57 (1H, q), 6.03 (1H, br), 6.27 (1H, s), 10.4-10.45 (1H, br), 11.31. -11.42 (1H, br).

<Synthesis of Compound 11>
Compound 10 (372.3 g) and 79.8 g of 3-mercapto-1-propanol were dissolved in 1 L of N-methylpyrrolidone (NMP), stirred at room temperature, and 1,8-diazabicyclo [5.4.0] undeca. 133.4 g of -7-ene (DBU) was added dropwise, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was poured into 1.5 L of ethyl acetate and 1.5 L of water, then washed with 1 L of 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate, water and saturated brine, and the organic layer was dehydrated with 50 g of magnesium sulfate and filtered. The filtrate was concentrated to dryness. The residue was dispersed and washed with 300 ml of acetonitrile, and the solid was collected by filtration and washed with 30 ml of acetonitrile to obtain Compound 11 (317 g).
Compound 11: ¹ H-NMR, 400 MHz, δ (CDCl 3) ppm: 0.9 (18 H, s), 1.02-1.03 (3 H, d), 1.21-1.22 (6 H, d) 1.23-1.41 (5H, m), 1.56-1.57 (3H, d), 1.6-1.63 (2H, br), 1.79-1.89 (2H, m), 2.72-2.78 (2H, t), 3.43-3.47 (1H, m), 3.51-3.55 (1H, q), 3.78-3.73 ( 2H, q), 6.0 (1H, s), 6.23 (1H, s), 10.51-10.55 (1H, br), 11.21-11.29 (1H, br).

<Synthesis of Compound 12>
Compound 11 (30 g) and 0.1 ml of nitrobenzene were dissolved in 250 ml of DMAc, 14.1 g of methacrylic acid chloride was added dropwise, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was added to 1.5 L of ethyl acetate and 1.5 L of water, extracted into the organic phase, and washed twice with 400 ml each of 1N hydrochloric acid, saturated aqueous sodium hydrogen carbonate, saturated brine, and water. The organic layer was dehydrated with 30 g of magnesium sulfate and filtered, and then the filtrate was concentrated to dryness to obtain Compound 12 (27.9 g).
Compound 12: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.9 (18H, s), 1.02-1.03 (3H, d), 1.21-1.22 (6H, d ), 1.23-1.41 (5H, m), 1.56-1.57 (3H, d), 1.6-1.63 (2H, br), 1.9 (3H, s) 1 .93-2.02 (2H, m), 2.6-2.73 (2H, t), 3.42-3.5 (1H, m), 3.51-3.56 (1H, q) 4.06-4.12 (1H, q), 4.14-4.23 (2H, t), 5.5 (1H, s), 6.11-6.15 (2H, m), 6 .23 (1H, s), 10.2-10.48 (1H, br), 11.28-11.32 (1H, br).

<Synthesis of Compound 13>
Compound 9 (263.6 g) was stirred in 800 ml of DMAc at room temperature, 5-chlorovaleric acid chloride (108.5 g) was added dropwise over 2 hours under ice cooling, and then stirred at room temperature for 3 hours. The reaction solution was poured into 18 L of water, the precipitated crystals were filtered off, and the obtained crystals were dispersed and washed with 1 L of acetonitrile to obtain Compound 13 (313 g).
Compound 13: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.9 (18H, s), 0.96-1.01 (3H, d), 1.20-1.75 (17H, m ) 1.76-2.00 (2H, m), 2.41-2.53 (2H, m), 3.4-3.58 (1H, m), 3.54-3.60 (2H) M), 6.0 (1H, br), 6.22 (1H, s), 10.55 (2H, br).

<Synthesis of Compound 14>
While stirring N-methylformanilide (66.2 g) and 330 ml of acetonitrile at 0 ° C. while keeping phosphorus oxychloride (75 g) at 5 ° C. or lower, and stirring for 1 hour, compound 13 (202 g) was added. After stirring at room temperature for 3 hours, the mixture was stirred at 40 ° C. for 1 hour. The reaction solution was poured into 2 L of water, and the precipitated crystals were filtered and washed with 500 ml of water and 500 ml of methanol to obtain Compound 14 (181 g).
Compound 14: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.9 (18H, s), 0.96-1.21 (3H, d), 1.22-1.76 (17H, m ), 1.78-2.22 (2H, m), 2.45-2.55 (2H, m), 3.4-3.58 (1H, m), 3.54-3.60 (2H) M), 6.3 (1H, br), 9.88 (1H, s), 11.09 (1H, br), 11.47 (1H, br).

<Synthesis of Compound 15>
Compound 14 (300 g) and thiomalic acid (129 g) were added to DMAc3L and stirred at room temperature, and dropwise over 30 minutes while keeping DBU (434 g) at 30 ° C. or lower. Thereafter, the mixture was stirred at 60 ° C. for 5 hours, 103 g of sodium hydroxide was dissolved in 600 ml of water, added dropwise to the reaction solution over 10 minutes, then cooled to room temperature, the precipitated crystals were filtered, and 1 L of ethyl acetate was added to 5 ° C. Washed with 200 ml of each cooled methanol. Disperse the crystals obtained in 1 L of ethyl acetate and 1 L of water, add 220 ml of concentrated hydrochloric acid to dissolve in the organic phase, then wash twice with 1 L of water and once with 1 L of saturated brine, and dry with 80 g of magnesium sulfate. Thereafter, the mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain Compound 15 (255 g).
Compound 15: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.9 (18H, s), 0.96-1.21 (3H, d), 1.22-1.76 (17H, m ), 1.78-2.22 (2H, m), 2.45-2.65 (4H, m), 3.35-3.61 (2H, m), 3.54-3.60 (2H) M), 6.3 (1H, br), 9.92 (1H, s), 11.11 (1H, br), 11.81 (1H, br).

<Synthesis of Compound 16>
Compound 12 (8.27 g), Compound 15 (8.92 g) and 45 ml of acetic anhydride were stirred at room temperature, 5.39 ml of trifluoroacetic acid was added dropwise under ice cooling, and the mixture was stirred at room temperature for 3 hours. An aqueous solution in which 400 ml of water, 60 g of sodium hydrogen carbonate and 3 drops of pyridine were added was stirred at room temperature, and the reaction solution was added dropwise to neutralize it, followed by stirring at room temperature for 3 hours. The precipitated crystals were separated by filtration, washed with water, and dried by blowing to obtain Compound 16 (16 g).
Compound 16: ¹ H-NMR, 400 MHz, δ (CDCl ₃ ) ppm: 0.92 (36H, s), 0.96-2.0 (44H, m), 2.04 (3H, s) 62-2.83 (3H, m), 2.97-3.56 (7H, m), 4.14-4.27 (1H, m), 5.0 (1H, br), 6.05 ( 3H, br), 7.52-7.56 (1H, br), 10.25-10.89 (1H, br), 11.34-11.56 (1H, br).

<Synthesis of Dye Monomer J-1>
Compound 16 (12.6 g), 150 ml of methanol and 75 ml of tetrahydrofuran were stirred at room temperature, zinc acetate dihydrate (2.2 g) was added, and the mixture was stirred for 2 hours. Thereafter, 500 ml of water was added to the reaction solution, and the precipitated crystals were filtered and air-dried to obtain Dye Monomer J-1 (13 g).
J-1: ¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.97 (36H, s), 0.99-2.05 (47H, m), 2.07-3.05 ( 8H, m), 4.04-4.4 (3H, m), 5.53 (1H, br), 6.05-6.12 (3H, br), 8.8 (1H, s), 10 97-11.18 (1H, br), 11.91-12.01 (1H, br).

  Subsequently, Exemplified Compound 114 was obtained from Dye Monomer J-1 by the following method according to the following synthesis scheme.

J-1 (11.7 g), methacrylic acid (1.58 g) and dodecanethiol (0.56 g) were dissolved in 75.0 g of propylene glycol monomethyl ether acetate (PGMEA) and stirred at 85 ° C. (23.6 g), methacrylic acid (3.16 g), dodecanethiol (1.11 g) and dimethyl 2,2′-azobis (2-methylpropionate) (3.8 g) dissolved in 150 g of PGMEA The solution was added dropwise over 3 hours. Four hours after the start of dropping, dimethyl 2,2′-azobis (2-methylpropionate) (1.14 g) was added, and stirring was continued at 85 ° C. for another 2 hours. To the reaction solution, 811 ml of PGMEA and 1081 ml of methanol were added, and the reaction solution was added dropwise to 4326 ml of acetonitrile. The precipitated crystals were filtered and the obtained crystals were dried under reduced pressure to obtain 13.8 g of Compound J-2.
The structure of Compound J-2 was confirmed by ¹ H-NMR to confirm the disappearance of the peak of 5.56-6.12 which is the polymerizable group site of Dye Monomer J-1, and the introduction of methacrylic acid by acid value measurement. Confirmed and confirmed.

Compound J-2 (10.0 g), glycidyl methacrylate (1.14 g), tetrabutylammonium bromide (0.21 g) and p-methoxyphenol (0.01 g) were dissolved in 63.1 g of PGMEA, Stir for hours. After the reaction solution was lowered to 30 ° C., the reaction solution was dropped into 1200 ml of acetonitrile. The precipitated crystals were filtered and the obtained crystals were dried under reduced pressure to obtain 8.8 g of Exemplified Compound 114.
The structure of the exemplary compound 114 was confirmed by ¹ H-NMR by confirming the peak of the polymerizable group site derived from glycididyl methacrylate and by measuring the acid value.

[Synthesis Example 3]
<Synthesis of Exemplary Compound 116>
The exemplary compound 116 of the polymerizable group-containing dye multimer was synthesized by the method described below according to the following synthesis scheme.

Dye monomer Q-1 was the same except that 3-mercapto-1-propanol used in the synthesis of Compound 11 which was an intermediate of the dye monomer J-1 was changed to 2-mercaptoethanol. Synthesized. The structure of Q-1 was confirmed by ¹ H-NMR.
Q-1: ¹ H-NMR, 400 MHz, δ (DMSO-d ₆ ) ppm: 0.91 (36H, s), 1.15 (6H, d), 1.21-2.17 (40H, m) 2.07-3.05 (6H, m), 3.61-3.84 (2H, m), 4.28-4.33 (3H, m), 5.56 (1H, br), 6 .01-6.12 (3H, br), 7.78 (1H, s), 11.03 (1H, br), 11.83-12.25 (1H, br).

Q-1 (13.3 g), methacrylic acid (1.58 g) and dodecanethiol (0.56 g) were dissolved in 75.0 g of PGMEA and stirred at 85 ° C., while Q-1 (23.3 g) and methacrylic acid were dissolved. A solution prepared by dissolving 3.16 g, dodecanethiol (1.11 g) and dimethyl 2,2′-azobis (2-methylpropionate) (3.8 g) in 150 g of PGMEA was added dropwise over 3 hours. Four hours after the start of dropping, dimethyl 2,2′-azobis (2-methylpropionate) (1.14 g) was added, and stirring was continued at 85 ° C. for another 2 hours. To the reaction solution, 811 ml of PGMEA and 1081 ml of methanol were added, and the reaction solution was added dropwise to 4326 ml of acetonitrile. The precipitated crystals were filtered and the obtained crystals were dried under reduced pressure to obtain 13.2 g of Compound Q-2.
The structure of compound Q-2 was confirmed by ¹ H-NMR to confirm the disappearance of the peak of 5.56-6.12, which is the polymerizable group site of dye monomer Q-1, and introduced methacrylic acid by acid value measurement. Confirmed and confirmed.

Compound Q-2 (10.0 g), glycidyl methacrylate (1.13 g), tetrabutylammonium bromide (0.2 g) and p-methoxyphenol (0.01 g) were dissolved in 63 g of PGMEA and stirred at 100 ° C. for 5 hours. did. After the reaction solution was lowered to 30 ° C., the reaction solution was dropped into 1200 ml of acetonitrile. The precipitated crystals were filtered, and the obtained crystals were dried under reduced pressure to obtain 8.7 g of Exemplary Compound 116.
The structure of the exemplary compound 116 was confirmed by ¹ H-NMR by confirming the peak of the polymerizable group site derived from glycididyl methacrylate and by measuring the acid value.

[Example 1]
<Formation of colored pattern using colored curable composition>
(1) Preparation of resist solution A (negative type)
The following components were mixed and dissolved to prepare a resist solution A.
Propylene glycol monomethyl ether acetate 5.20 partsCyclohexanone 52.60 partsBinder 30.50 parts (benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer (mass% ratio = 60: 20: 20 ), Average molecular weight 30200 (polystyrene conversion), 41% cyclohexanone solution)
Dipentaerythritol hexaacrylate 10.20 parts Polymerization inhibitor (p-methoxyphenol) 0.006 parts Fluorosurfactant (F-475 manufactured by DIC Corporation) 0.80 parts Photopolymerization initiator: 4-Benzoxolane-2,6-bis (trichloromethyl) -s-triazine (manufactured by Midori Chemical Co., Ltd. TAZ-107) 0.58 parts

(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 (1) above was applied on a glass substrate washed with a spin coater so that the film thickness after drying was 2 μm, and was dried by heating at 220 ° C. for 1 hour, with an undercoat layer. A glass substrate was prepared.

(3) Preparation of colored curable composition The following components were mixed and dissolved to prepare a colored curable composition.
Propylene glycol monomethyl ether acetate 80 parts Polymerizable compound: Dipentaerythritol hexaacrylate 14.0 parts Polymerization inhibitor: p-methoxyphenol 0.006 parts Fluorine-based surfactant (F-475 manufactured by DIC Corporation) ) 0.80 parts Photopolymerization initiator (manufactured by Midori Chemical Co., Ltd. TAZ-107) 2.0 parts Exemplified compound 109 4.0 parts (added as 30% by mass propylene glycol monomethyl ether acetate solution)

(4) Formation of colored pattern The colored curable composition obtained in (3) above has a thickness of 0.6 μm after drying on the undercoat layer of the glass substrate with undercoat layer obtained in (2) above. This was applied using a spin coater and pre-baked 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.
The red pattern which comprises a color filter was obtained as mentioned above.
FIG. 2 shows a transmission spectrum of the produced red pattern region.

(5) Evaluation Storage stability with time of the colored curable composition prepared above, and heat resistance, light resistance, and solvent resistance of the coating film coated on the glass substrate using the colored curable composition The properties and pattern shapes were evaluated as follows. The evaluation results are shown in Table 3 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 fastness. 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-
A: ΔE ^* ab value <3
○: 3 ≦ 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-
A: ΔE ^* ab value <3
○: 3 ≦ ΔE ^* ab value <5
Δ: 5 ≦ ΔE ^* ab value ≦ 12
×: ΔE ^* ab value> 12

[Solvent resistance]
The spectrum of the coating film after post-baking obtained in the above (4) 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 using a developer under the conditions of 23 ° C. and 120 seconds, and the spectrum was measured again (spectrum B). The dye residual ratio (%) was calculated from the difference between the spectra A and B and used as an index for evaluating the solvent resistance. This value indicates that the closer to 100%, the better the solvent resistance.
-Criteria-
A: Dye remaining rate> 95%
○: 90% <dye residual ratio ≦ 95%
Δ: 70% ≦ dye residual rate ≦ 90%
X: Dye residual ratio <70%

[Pattern shape]
The development pattern of the post-baked coating film obtained in (4) above is observed with an optical microscope (Olympus Digital Microscope RX-20), and whether or not a fine pattern is formed is determined as follows. Evaluation was made according to criteria.
-Criteria-
○: No chipping was observed at the edge of the pattern.
(Triangle | delta): Although the pattern was formed, the crack was recognized by the edge of the pattern.
X: A pattern was not formed.

[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 109 was changed to a pigment described in Table 3 below (but equivalent mass). Furthermore, the same evaluation was performed. The evaluation results are shown in Table 3 below.

  In addition to the propylene glycol monomethyl ether acetate used in the examples, the polymerizable group-containing dye multimer according to the present invention can be dissolved in various organic solvents (for example, ethyl lactate and cyclohexanone having higher safety). It was very effective and was effective in reducing work load from the viewpoint of work safety.

[Comparative Examples 1 and 2]
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 109 was changed to the following comparative dye 1 or 2 (but equal mass). The same evaluation was performed. The evaluation results are shown in Table 3 below together with the results of the examples.

  As shown in Table 3, in Examples 1 to 12 of the present invention, compared with Comparative Examples 1 and 2, the colored curable composition has excellent storage stability over time, and the coating film has good heat resistance and light resistance. Solvent resistance and pattern shape were shown.

[Examples 113 to 126, Comparative Example 13]
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 109 was changed to the dye (but equivalent mass) described in Table 4 below. Furthermore, the same evaluation was performed. The evaluation results are shown in Table 4 below. In addition, the comparative pigment | dye 3 in following Table 4 is the following compound.

  As shown in Table 4, in Examples 113 to 126 of the present invention, compared with Comparative Example 13, the colored curable composition is excellent in storage stability with time, and the coating film has good heat resistance, light resistance, resistance to light. Solvent property and pattern shape were shown.

[Examples 13 to 24, Comparative Examples 3 and 4, and Examples 25 to 36, Comparative Examples 5 and 6]
<Preparation of single color filter>
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 24 and Comparative Examples 3 and 4. Carried out. The evaluation results are shown in Table 5 below.
At the same time, a color filter was prepared without performing the ultraviolet irradiation step after the development step, and Examples 25-36 and Comparative Examples 5 and 6 were carried out to evaluate the color transfer. The evaluation results are shown in Table 5 below.

(1) Production 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.

(2) Exposure / development of colored curable composition Next, using the colored curable compositions used in Examples 1 to 12 and Comparative Examples 1 and 2, the undercoat layer of the obtained silicon wafer with an undercoat layer was used. On top of this, a spin coater was applied so that the dry film thickness was 1 μm, and prebaked at 100 ° C. for 120 seconds to form a colored film on the silicon wafer. With respect to this colored film, 200 μm is obtained by an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.) through a mask pattern in which 2.0 μm square pixels are arranged in a 4 mm × 3 mm region on the substrate. 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 (Fuji Film Electronics Materials Co., Ltd. CD-2000, 60%) 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 silicon wafer 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 silicon wafer. The irradiation illuminance [mW / cm ² ] of light having a wavelength of 275 nm or less included in the irradiation light from the high-pressure mercury lamp is 10% with respect to the integrated irradiation illuminance of all wavelength light in the ultraviolet light.
As described above, monochromatic color filters of Examples 13 to 24 and Comparative Examples 3 and 4 were produced. Moreover, the monochrome color filter of Examples 25-36 and Comparative Examples 5 and 6 was produced, without performing the ultraviolet irradiation after a image development process.

(3) Evaluation The color migration of the color filter produced as described above was evaluated as follows.
A CT-2000L solution (manufactured by FUJIFILM Electronics Materials Co., Ltd .; transparent base material) was applied to the color pattern forming surface of the color filter so that the dry film thickness was 1 μm, and dried to form a transparent film. Thereafter, heat treatment was performed at 200 ° C. for 5 minutes. After heating, the absorbance of the transparent film adjacent to the colored pattern was measured with MCPD-3000 (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 to the adjacent pixels.
-Criteria-
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%

  As shown in Table 5, in Examples 13 to 36 of the present invention, color transfer to adjacent pixels was suppressed.

[Examples 127 to 140, Comparative Example 14, and Examples 141 to 154, Comparative Example 15]
Using the colored curable composition used in Examples 113 to 126 and Comparative Example 13, color filters were prepared in the same manner as in Example 13 and the like, and color transfer as Examples 127 to 140 and Comparative Example 14 was performed. Evaluation was performed. The evaluation results are shown in Table 6 below.
At the same time, a color filter was produced without performing the ultraviolet irradiation step after the development step, and Examples 141 to 154 and Comparative Example 15 were carried out to evaluate the color transfer. The evaluation results are shown in Table 6 below.

  As shown in Table 6, in Examples 127 to 154 of the present invention, color transfer to adjacent pixels was suppressed.

[Examples 37 to 48, Examples 155 to 168]
<Preparation of color filter for solid-state image sensor>
(1) Production of silicon wafer substrate with undercoat layer A 6-inch silicon wafer was heat-treated at 200 ° C. for 30 minutes in an oven. 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.

(2) Preparation of color filter pattern for solid-state imaging device Each colored curable composition used in Examples 1-12 and Examples 113-126 on the undercoat layer of the obtained silicon wafer substrate with an undercoat layer, Each of the coating films was applied so that the dry film thickness was 0.8 μm to form a photocurable coating film. 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 12 and Examples 113 to 126 is square and has a rectangular cross-sectional shape, which is suitable for a solid-state imaging device. Showed a good profile.

[Examples 49 to 51, Examples 169 to 172]
In Example 1, Exemplified Compound 109 was changed to the dyes listed in Table 7 below, and photopolymerization initiator: 4-benzoxolane-2,6-bis (trichloromethyl) -s-triazine (Midori Chemical Co., Ltd.) A pattern was formed in the same manner as in Example 1 except that TAZ-107) was changed to the following oxime initiator (I-1) or (I-2), and the same evaluation was performed. The evaluation results are shown in Table 7 below.

  From the results in Table 7, it can be seen that by using an oxime-based initiator as the photopolymerization initiator, performances such as heat resistance, solvent resistance, and pattern shape are further improved to the same or better levels.

Claims (13)

(A) has a A zone dye and group derived from a dye selected from dipyrromethene dye, further dye multimer having a polymerizable group, and (B) a colored curable composition containing a polymerizable compound.   2. The colored curable composition according to claim 1, wherein the dye multimer includes a structural unit having a polymerizable group and a structural unit having a group derived from a dye selected from an azo dye and a dipyrromethene dye as a repeating unit. object. The colored curable composition according to claim 2, wherein the dye multimer contains 1% by mass or more of a structural unit having a polymerizable group. The colored curable composition according to any one of claims 1 to 3, wherein the polymerizable group is an ethylenically unsaturated group. The colored curable composition according to any one of claims 1 to 4 , wherein the dipyrromethene dye is a dipyrromethene dye in which a compound represented by the following general formula (1) is coordinated to a metal atom or a metal compound. .

[In General Formula (1), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Represents. ] The colored curable composition according to claim 5 , wherein the dipyrromethene dye is a dipyrromethene dye represented by the following general formula (C).

[In General Formula (C), R ^{2 to} R ⁵ each independently represents a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic ring. Represents a group. Ma represents a metal or a metal compound. X ³ and X ⁴ each independently represent NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, Or represents a sulfur atom. Y ¹ represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), or a nitrogen atom. Y ² represents a nitrogen atom or a carbon atom. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-, 6-, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. ] The colored curable composition according to any one of claims 1 to 6 , further comprising (C) a polymerization initiator and (D) a solvent. A color resist comprising the colored curable composition according to any one of claims 1 to 7 and used for forming a colored pixel by a photolithography method. A color filter using the colored curable composition according to any one of claims 1 to 7 . A colored layer forming step of forming a colored layer by applying the colored curable composition according to any one of claims 1 to 7 on a support, and a pattern with respect to the colored layer through a mask A method for producing a color filter, comprising: an exposure step of performing a similar exposure to form a latent image; and a development step of developing a colored layer on which the latent image is formed to form a pattern. The method for producing a color filter according to claim 10 , further comprising an ultraviolet irradiation step of irradiating the formed pattern with ultraviolet rays after the developing step. A solid-state imaging device comprising the color filter according to claim 9 . An image display device comprising the color filter according to claim 9 .