JP2011202025A - Solid dispersion, colored photosensitive composition, inkjet ink, color filter and method for manufacturing the same, solid imaging element, display, metal complex compound, and its tautomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid dispersion formable of a colored film having excellent color purity and fastness.SOLUTION: In the solid dispersion containing a solvent and a coloring agent insoluble in the solvent, the coloring agent is a complex wherein a compound represented by general formula (1) or its tautomer is coordinated to a metal or a metal compound and which is insoluble in the solvent or a complex formed by insolubilizing a complex wherein a compound represented by general formula (1) or its tautomer is coordinated to a metal or a metal compound to the solvent (in formula, Rto Reach denotes a hydrogen atom or a substitution group, and Rdenotes a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a hetero ring group).

Description

  The present invention relates to a solid dispersion, a colored photosensitive composition, an inkjet ink, a color filter and a method for producing the same, a solid-state imaging device, a display device, a metal complex compound, and a tautomer thereof.

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

  The colorant used in the color filter is commonly required to have the following characteristics. In other words, it has optical characteristics that are favorable for color reproducibility, optical scattering such as light scattering that causes a decrease in contrast of a liquid crystal display, and unevenness in optical density that causes color unevenness and roughness of a solid-state imaging device. There is a need for a high degree of fastness, such as heat resistance, light resistance, moisture resistance, and the like, a large molar extinction coefficient, and a thin film.

As one of the methods for producing the color filter, a pigment dispersion method is employed.
A method for producing a color filter by a photolithographic method or an inkjet method using a colored photosensitive composition in which a pigment is dispersed in a photosensitive composition by a pigment dispersion method is stable against light and heat because the pigment is used. It is.

  In this photolithography method, a radiation-sensitive composition is applied onto a substrate by a spin coater, a roll coater, or the like, dried to form a coating film, and the coating film is subjected to pattern exposure and development, whereby colored pixels are formed. obtain. By repeating this operation for the hue, a color filter can be produced. The photolithographic method is widely used as a method suitable for the production of a color filter having a large screen and high definition because it forms a pattern with light and has excellent positional accuracy. In particular, this is a very advantageous method for producing a solid-state imaging device that requires higher resolution in recent years.

In addition to the photolithographic method, a method for forming a colored layer (colored pixel) by spraying colored ink by an inkjet method has been proposed as a method for producing a color filter (see, for example, Patent Documents 1 and 2). .)
The ink jet method is a recording method in which characters and images are obtained by ejecting and adhering ink droplets directly from a very fine nozzle to a recording member. The ink jet method has an advantage that a color filter having a large area can be manufactured with high productivity by sequentially moving the ink jet head, and the operability is low with low noise. Ink jet ink using a pigment dispersion method is used for manufacturing a color filter by such an ink jet method. As an inkjet ink using the pigment dispersion method, for example, an inkjet ink for a color filter containing a binder component, a pigment, and a solvent having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 0.5 mmHg or less. Proposed.

On the other hand, a technique for forming a color filter by a photolithographic method using a colored photosensitive composition containing a dye instead of a pigment in order to suppress resolution reduction and color unevenness due to the influence of coarse particles of the pigment is also being studied. .
For example, focusing on spectral characteristics suitable for color filters, colored photosensitive compositions and pigment compounds using dipyrromethene dyes have been studied (for example, see Patent Document 3).

JP 59-75205 A JP 2004-339332 A JP 2008-292970 A

In a coloring composition for a color filter containing a dye, a phenomenon in which the color of the colored film moves to an adjacent layer or a laminated layer (hereinafter referred to as “color”, particularly when heat treatment is performed after the colored film is formed). There is a tendency to occur easily.
Patent Document 3 discloses a spectral characteristic derived from a light absorption characteristic unique to a dipyrromethene dye, but does not mention the above-described color transfer.
Further, in the dipyrromethene dye described in Patent Document 3, further improvements in various fastnesses such as heat resistance and light resistance are desired.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a solid dispersion capable of forming a colored film excellent in color purity and fastness.
Another object of the present invention is to provide a colored photosensitive composition capable of forming a colored pattern with suppressed color transfer and excellent color purity and fastness.
Another object of the present invention is to provide an inkjet ink that can form colored pixels having excellent color purity and fastness.
Another object of the present invention is to provide a color filter excellent in color purity and fastness, a method for manufacturing the same, and a solid-state imaging device and a display device including the color filter.
Another object of the present invention is to provide a metal complex compound excellent in color purity and fastness and a tautomer thereof.

As a result of detailed examination of the dipyrromethene metal complex, the present inventors have found that a dipyrromethene metal complex insoluble in the solvent or a dipyrromethene metal complex insolubilized in the solvent (for example, lake) is solidified in the solvent. The knowledge that a colored film excellent in color purity and fastness can be formed by using a solid dispersion obtained by dispersion was obtained, and the present invention was completed based on this knowledge.
Specific means for solving the above problems are as follows.

<1> containing a solvent and a colorant insoluble in the solvent,
The colorant is a complex in which a compound represented by the following general formula (1) or a tautomer thereof is coordinated to a metal or a metal compound and is insoluble in the solvent, or the following general A solid dispersion, wherein the complex represented by the formula (1) or a tautomer thereof is coordinated to a metal or a metal compound and is insolubilized in the solvent.

[In General Formula (1), R < ¹ > -R < ⁶ > represents a hydrogen atom or a substituent each independently. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. ]

<2> A complex in which a compound represented by the general formula (1) or a tautomer thereof is coordinated to a metal or a metal compound is insolubilized in the solvent is represented by the following general formula (2). <1> which is a metal complex compound or a tautomer thereof.

[In general formula (2), A removed one hydrogen atom from any position of the complex represented by the compound represented by general formula (1) or a tautomer thereof coordinated to a metal or a metal compound. It is a residue, n represents 2 or 3, and M represents an n-valent metal ion. ]

<3> The compound represented by the general formula (1) or a tautomer thereof is coordinated to a metal or a metal compound is a compound represented by the following general formula (2) or a tautomer thereof. The solid dispersion according to <1> or <2>.

[In General Formula (3), R ^{2 to} R ⁵ each independently represents a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal or a metal compound, and X ³ represents 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), nitrogen. An atom, an oxygen atom, or a sulfur atom, and X ⁴ represents NRa (Ra 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); Represents an oxygen atom or a sulfur atom, and 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), a nitrogen atom. , or represents a carbon atom, Y ² is a nitrogen atom, or represents a carbon atom, R ⁸ and R ⁹ are each independently an alkyl group, an alkenyl group, aryl It represents 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-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. ]

<4> A colored photosensitive composition comprising the solid dispersion according to any one of <1> to <3>.
<5> An inkjet ink containing the solid dispersion according to any one of <1> to <3>.
<6> A color filter using the colored photosensitive composition according to <4> or the inkjet ink according to <5>.
<7> The step of applying the colored photosensitive composition according to <4> on a support to form a colored layer, the step of exposing the formed colored layer through a mask, and the exposed colored layer And developing a color pattern to form a color pattern.
<8> The method for producing a color filter according to <7>, further comprising a step of irradiating the formed colored pattern with ultraviolet rays after the step of forming the colored pattern.
<9> A step of preparing a substrate having a recess partitioned by a partition, and applying the ink-jet ink droplet according to <8> to the recess by an inkjet method to form a colored pixel of a color filter And a process for producing a color filter.
<10> A solid-state imaging device comprising the color filter according to <6>.
<11> A display device comprising the color filter according to <6>.
<12> A metal complex compound represented by the following general formula (2) and a tautomer thereof.

[In general formula (2), A removed one hydrogen atom from an arbitrary position of a complex represented by the following general formula (1) or a tautomer thereof coordinated to a metal or a metal compound. It is a residue, n represents 2 or 3, and M represents an n-valent metal ion. ]

[In General Formula (1), R < ¹ > -R < ⁶ > represents a hydrogen atom or a substituent each independently. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. ]

<13> A compound represented by the general formula (1) or a tautomer thereof coordinated to a metal or a metal compound is a compound represented by the following general formula (3) or a tautomer thereof. The metal complex compound according to <12> and a tautomer thereof.

[In General Formula (3), R ^{2 to} R ⁵ each independently represents a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal or a metal compound, and X ³ represents 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), nitrogen. An atom, an oxygen atom, or a sulfur atom, and X ⁴ represents NRa (Ra 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); Represents an oxygen atom or a sulfur atom, and 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), a nitrogen atom. , or represents a carbon atom, Y ² is a nitrogen atom, or represents a carbon atom, R ⁸ and R ⁹ are each independently an alkyl group, an alkenyl group, aryl It represents 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-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. ]

ADVANTAGE OF THE INVENTION According to this invention, the solid dispersion liquid which can form the colored film excellent in color purity and fastness can be provided.
In addition, according to the present invention, it is possible to provide a colored photosensitive composition capable of forming a colored pattern with suppressed color transfer and excellent color purity and fastness.
Moreover, according to this invention, the ink for inkjets which can form the colored pixel excellent in color purity and fastness can be provided.
In addition, according to the present invention, it is possible to provide a color filter excellent in color purity and fastness, a manufacturing method thereof, and a solid-state imaging device and a display device including the color filter.
Moreover, according to this invention, the metal complex compound excellent in color purity and fastness, and its tautomer can be provided.

Hereinafter, although embodiment of this invention is described, this invention is not limited to the following embodiment.
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.

≪Solid dispersion≫
The solid dispersion of the present invention contains a solvent and a colorant insoluble in the solvent (hereinafter also referred to as “specific colorant”), and the colorant is represented by the following general formula (1). Is a complex coordinated to a metal or a metal compound (hereinafter also referred to as “specific complex”) and is insoluble in the solvent (metal complex compound), or the specific complex is added to the solvent. It is a complex (metal complex compound) insolubilized.
That is, in the solid dispersion of the present invention, the specific colorant is dispersed as a solid (pigment) in the solvent.
By setting the solid dispersion to the structure of the present invention, fastness (heat resistance and light resistance) can be improved while maintaining the good color purity of the specific complex.
Therefore, according to the solid dispersion of the present invention, a colored film having excellent color purity and fastness can be formed.
Furthermore, the solid dispersion of the present invention is excellent in storage stability.
As described above, the solid dispersion of the present invention is suitably used for the colored photosensitive composition of the present invention described later and the inkjet ink of the present invention.

Further, according to the study by the present inventors, the specific colorant is solid-dispersed in the solvent without using a dispersant (even if used, in a content of 10% by mass or less in the total solid content of the solid dispersion). I found out that I could do it.
Thereby, as described later, it was found that various effects such as a reduction in the thickness of the formed colored film (colored pattern, colored pixel, etc.), improvement in sensitivity and pattern formability can be obtained.
Hereinafter, the colorant contained in the solid dispersion of the present invention will be described first.

<Colorant>
The colorant (specific colorant) in the present invention is a complex (specific complex) in which the compound represented by the following general formula (1) is coordinated to a metal or a metal compound, and is included in the solid dispersion of the present invention. Or a complex (metal complex compound) in which the specific complex is insolubilized in the solvent.
In the present invention, “insolubilized”, “insoluble” or “not dissolved” refers to a state where the solubility in a solvent at 25 ° C. is 1% by mass or less. The solubility is preferably 0.5% by mass or less, more preferably 0.25% by mass or less, and particularly preferably 0.1% by mass or less. A specific form of insolubilization will be described later.
Hereinafter, the specific complex will be described first.

(Specific complex)
-Compound represented by the general formula (1)-
The specific complex in the present invention is a complex in which a compound represented by the following general formula (1) (dipyrromethene compound) or a tautomer thereof is coordinated to a metal or a metal compound.

R < ¹ > -R < ⁶ > in General formula (1) represents a hydrogen atom or a substituent each independently. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Examples of the substituent in R ^{1 to} R ⁶ in the general formula (1) include a halogen atom (for example, fluorine, chlorine, bromine) and an alkyl group (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). A linear, branched or cyclic alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, Cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, for example, vinyl, allyl, 3-buten-1-yl ), An aryl group (preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, Phenyl, naphthyl), a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1 -Pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-1-yl), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, for example, trimethylsilyl , Triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxyl group, cyano group, nitro group, alkoxy group (preferably having 1 to 48 carbon atoms, more preferably having 1 to 24 carbon atoms) Groups such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t A butoxy, dodecyloxy, cycloalkyloxy group such as cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenoxy, 1-naphthoxy), 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 and 2-tetrahydropyranyloxy ), A silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy), an acyloxy group (preferably carbon 2 to 48, more preferably 2 to 2 carbon atoms 4 is an acyloxy group, for example, acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, Ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy group, for example, cyclohexyloxycarbonyloxy), aryloxycarbonyloxy group (preferably having 7 to 32 carbon atoms, more preferably aryl having 7 to 24 carbon atoms) An oxycarbonyloxy group such as phenoxycarbonyloxy), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably a carbamoyloxy group having 1 to 24 carbon atoms such as N, N-dimethyl Rubamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), a sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms). Moyloxy group, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably having 1 to 24 carbon atoms) An oxy group, for example, methylsulfonyloxy, hexadecylsulfonyloxy, cyclohexylsulfonyloxy),

  An arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as phenylsulfonyloxy), an acyl group (preferably having 1 to 48 carbon atoms, more preferably carbon An acyl group having 1 to 24, for example, formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl, cyclohexanoyl), an alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably an alkoxy having 2 to 24 carbon atoms) Examples of carbonyl groups include methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl), and aryloxycarbonyl groups (preferably having 7 to 32 carbon atoms). , Yo Preferably, it is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as phenoxycarbonyl, and a carbamoyl group (preferably having 1 to 48 carbon atoms, more preferably a carbamoyl group having 1 to 24 carbon atoms, such as carbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N, N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methylN-phenylcarbamoyl, N, N-dicyclohexylcarbamoyl), amino A group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as amino, methylamino, N, N-dibutylamino, tetradecylamino, 2-ethylhexylamino, cyclohexylamino), anilino Group (preferably having 6 to 32 carbon atoms) More preferably, it is an anilino group having 6 to 24, for example, anilino or N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 heterocyclic amino group, for example, 4- Pyridylamino), a carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetamide, benzamide, tetradecanamide, pivaloylamide, cyclohexaneamide), a ureido group (preferably 1 carbon atom). To 32, more preferably a ureido group having 1 to 24 carbon atoms, such as ureido, N, N-dimethylureido, N-phenylureido), an imide group (preferably having 36 or less carbon atoms, more preferably having 24 or less carbon atoms). Imide groups such as N-succinimide and N-phthalimide), alkoxy Sicarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino, cyclohexyl Oxycarbonylamino), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), a sulfonamide group (preferably having a carbon number) 1 to 48, more preferably a sulfonamide group having 1 to 24 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexanesulfonamide A sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N-ethyl-N-dodecyl). Sulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenylazo, 3-pyrazolylazo),

  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, ethylthio, octylthio, cyclohexylthio), an arylthio group (preferably having 6 to 48 carbon atoms, more preferably An arylthio group having 6 to 24 carbon atoms, such as phenylthio, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, such as 2-benzothiazoli Ruthio, 2-pyridylthio, 1-phenyltetrazolylthio), an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, dodecanesulfinyl group), an arylsulfinyl group ( Preferably it has 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms. An arylsulfonyl group (for example, phenylsulfinyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, Isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, cyclohexylsulfonyl), an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfonyl, 1-naphthylsulfonyl), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as sulfamoyl, N, N-dipropylsulfa , N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl, N-cyclohexylsulfamoyl), sulfo group, phosphonyl group (preferably having 1 to 32 carbon atoms, more preferably carbon A phosphonyl group having 1 to 24 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), phosphinoylamino group (preferably having 1 to 32 carbon atoms, more preferably phosphino having 1 to 24 carbon atoms) An ylamino group represents, for example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino).

In the case where the substituents of R ^{1 to} R ^{6 in} the general formula (1) are further substitutable groups, the substituents described for R ^{1 to} R ⁶ may be included, and two or more substituents may be substituted. When it has a group, these 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 / or R ⁵ and R ⁶ are each independently bonded to each other to form 5 members, 6 members, or 7 members. A saturated ring or an unsaturated ring may be formed. When the 5-membered, 6-membered, and 7-membered rings formed are further substitutable groups, they may be substituted with the substituents described for R ^{1 to} R ⁶ above. When substituted with a substituent, these substituents may be the same or different.
R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and / or R ⁵ and R ^{6 in the} general formula (I) are each independently bonded to each other and have no substituent. When forming a 6-membered, 6-membered, or 7-membered saturated ring, or an unsaturated ring, examples of the 5-membered, 6-membered, or 7-membered saturated ring or unsaturated ring having no substituent include, for example, a pyrrole ring , Furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring, pyridazine ring, and preferably Includes a benzene ring and a pyridine ring.

R ⁷ in the general formula (1) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the halogen atom, alkyl group, or aryl group described above for the substituents of R ^{1 to} R ^6. And the same group as the heterocyclic group, and the preferred range thereof is also the same.
When the alkyl group, aryl group, and heterocyclic group of R ⁷ are further substitutable groups, they may be substituted with the substituents described for the substituents of R ^{1 to} R ^6. When substituted with the above substituents, these substituents may be the same or different.

~ Metal or metal compound ~
The specific complex in the present invention is a complex in which the compound represented by the above general formula (1) or a tautomer thereof is coordinated to a metal or a metal compound.
Here, the metal or metal compound may be any metal or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, Or a bivalent metal chloride is contained. As the metal or metal compound, for example, Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, etc., AlCl, InCl, FeCl, TiCl ₂ , Also included are metal chlorides such as SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ .
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex VO is preferred, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO is more preferred, and Zn is most preferred.

Next, the preferable range of the specific complex in this invention is demonstrated.
The preferred range of the specific complex in the present invention is that in general formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, Cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group , An aryloxycarbonylamino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, wherein R ² and R ⁵ are each Independently, hydrogen atom, halogen atom, alkyl group, alkenyl group, ant Group, heterocyclic group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino Group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ³ and R ⁴ are each independently a hydrogen atom or a halogen atom. , Alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamide Group, ureido group, imide group, al Alkoxycarbonylamino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl 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, and the metal or metal compound is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or VO. is there.

A more preferable range of the specific complex in the present invention is that in the general formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, or an 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, and 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, aryloxy group Carbonyl group, carbamoyl group, imide group, alkylsulfonyl group, aryl A sulfonyl group or a sulfamoyl group, wherein R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, A carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ⁷ is a hydrogen atom. , A halogen atom, an alkyl group, an aryl group, or a heterocyclic group, wherein the metal or metal compound is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO.

The particularly preferred range of the specific complex in the present invention is that in general formula (1), R ¹ and R ⁶ are each independently a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, A carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, and R ² and R ⁵ are each independently An alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group, and R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group , An aryl group, or a heterocyclic group, and R ⁷ is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group There is a range in which the metal or metal compound is Zn, Cu, Co, or VO.

-Compound represented by the general formula (3)-
As the specific complex in the present invention, a compound represented by the general formula (3) or a tautomer thereof is particularly preferable.

In General Formula (3), R ^{2 to} R ⁵ each independently represent a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal or a metal compound, and X ³ represents 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), nitrogen. An atom, an oxygen atom, or a sulfur atom, and X ⁴ represents NRa (Ra 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); Represents an oxygen atom or a sulfur atom, and 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), a nitrogen atom. , or represents a carbon atom, Y ² is a nitrogen atom, or represents a carbon atom, R ⁸ and R ⁹ are each independently an alkyl group, an alkenyl group, aryl It represents 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-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2.

R < ² > -R < ⁵ > and R < ⁷ > in General formula (3) are synonymous with R < ¹ > -R < ⁶ > and R < ⁷ > in General formula (1), A preferable aspect is also the same.
Ma in the general formula (3) represents a metal or a metal compound, and is synonymous with the metal or metal compound described in the description of the specific complex, and a preferable range thereof is also the same.

In the general formula (3), R ⁸ and R ⁹ are each independently an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms. 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, 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, for example, phenyl, naphthyl, etc. ), 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), an alkoxy group (preferably having 1 to 36 carbon atoms, more preferably 1 to 3 carbon atoms). 18 alkoxy groups such as methoxy, ethoxy, propyloxy, butoxy, hexyloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy), aryloxy (preferably having 6 to 24 carbon atoms, more preferably 1 to 18 carbon atoms). An aryloxy group, for example, phenoxy, naphthyloxy), an alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, for example, methylamino, ethylamino, propylamino, butylamino , Hexylamino, 2-ethylhexyl Silamino, isopropylamino, t-butylamino, t-octylamino, cyclohexylamino, N, N-diethylamino, N, N-dipropylamino, N, N-dibutylamino, N-methyl-N-ethylamino), aryl Amino (preferably an arylamino group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, for example, phenylamino, naphthylamino, N, N-diphenylamino, N-ethyl-N-phenylamino), or a heterocyclic ring An amino group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, for example, 2-aminopyrrole, 3-aminopyrazole, 2-aminopyridine, 3-aminopyridine) is represented.

In general formula (3), the alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, or heterocyclic amino group of R ⁸ and R ⁹ is further substituted. When it is a possible group, it may be substituted with the substituents described in the above R ^{1 to} R ⁶ , and when it is substituted with two or more substituents, those substituents are the same. It may or may not be.

In General Formula (3), X ³ represents NR, a nitrogen atom, an oxygen atom, or a sulfur atom, X ⁴ represents NRa, an oxygen atom, or a sulfur atom, and R and Ra are each independently 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), an alkenyl group (preferably 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 an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms such as phenyl, Til), 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), an acyl group (preferably an acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms such as acetyl, pivaloyl, 2-ethylhexyl) , Benzoyl, cyclohexanoyl), an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 24 carbon atoms, more preferably 1-18, for example, methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclohexylsulfonyl), arylsulfonyl group (Preferably having 6 to 24 carbon atoms, more preferably 6 to 18 arylsulfonyl groups, for example, phenylsulfonyl and naphthylsulfonyl).
The alkyl group, alkenyl group, aryl group, heterocyclic group, acyl group, alkylsulfonyl group, and arylsulfonyl group of R and Ra are further substituted with the groups described for the substituents of R ^{1 to} R ^6. In the case where it is substituted with a plurality of substituents, these substituents may be the same or different.

In General Formula (3), Y ¹ represents NRc, a nitrogen atom, or a carbon atom, Y ² represents a nitrogen atom or a carbon atom, and Rc has the same meaning as R in X ³ above.

In the general formula (3), R ⁸ and Y ¹ are bonded to each other, and together with R ⁸ , Y ¹ and the carbon atom, a 5-membered ring (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 A 7-membered ring (eg, cycloheptane, hexamethyleneimine) may be formed.

In General Formula (3), R ⁹ and Y ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with R ⁹ , Y ² , and the carbon atom. Examples of the 5-membered, 6-membered, and 7-membered rings that are formed include rings in which one bond is changed to a double bond from the ring formed by R ⁸ , Y ^1, and a carbon atom.

In the general formula (3), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ⁸ and Y ¹ and R ⁹ and Y ² are further substitutable rings, The substituents described above for the substituents of R ^{2 to} R ⁵ may be substituted, and when they are substituted with two or more substituents, these substituents may be the same or different. Good.

As a preferable aspect of the compound represented by the general formula (3), R ^{2 to} R ⁵ , R ⁷ , and Ma are each a preferable aspect described in the description of the specific complex, and X ³ is NR (R is A hydrogen atom, an alkyl group), a nitrogen atom, or an oxygen atom, X ⁴ is NRa (Ra is a hydrogen atom, an alkyl group, a heterocyclic group), or an oxygen atom, Y ¹ is NRc (Rc is a hydrogen atom, Or an alkyl group), a nitrogen atom, or a carbon atom, Y ² is a nitrogen atom or a carbon atom, X ⁵ is a group bonded through an oxygen atom, and R ⁸ and R ⁹ are each independently , An alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R ⁸ and Y ¹ are bonded to each other to form a 5-membered or 6-membered ring, or R ⁹ and Y ² are bonded to each other To form a 5-membered or 6-membered ring, and a is Or represented by 1.

As a further preferred embodiment of the compound represented by the general formula (3), R ^{2 to} R ⁵ , R ⁷ and Ma are particularly preferred embodiments described in the description of the compound represented by the general formula (1). , X ³ and X ⁴ are oxygen atoms, Y ¹ is NH, Y ² is a nitrogen atom, X ⁵ is a group bonded through an oxygen atom, and R ⁸ and R ⁹ are alkyl groups. Group, aryl group, heterocyclic group, alkoxy group, or alkylamino group, or R ⁸ and Y ¹ are bonded to each other to form a 5-membered or 6-membered ring, or R ⁹ and Y ² are bonded to each other. 5 and 6-membered rings are formed, and a is represented by 0 or 1.

The specific complex in the present invention has been described above.
The specific colorant in the present invention is the specific complex described above and is insoluble in the solvent contained in the solid dispersion of the present invention, or the specific complex described above is included in the solid dispersion of the present invention. It is a complex insolubilized in the solvent contained.

The “complex insoluble in the solvent” is not particularly limited as long as it is insoluble in relation to the solvent. For example, R ¹ in the general formula (1) so that the specific complex is insoluble in the solvent. To R ⁷ (or R ^{2 to} R ⁵ , R ^{7 to} R ⁹ , X ³ , X ⁴ , Y ¹ , Y ^{2 in} General Formula (3)) may be appropriately selected.
For example, when the solvent contains at least one selected from propylene glycol monomethyl ether acetate, ethyl lactate, and cyclohexanone, a preferable form of “a complex insoluble in the solvent” is R ¹ in the general formula (1). To R ⁶ (or R ^{2 to} R ⁵ , R ⁸ , R ^{9 in the} general formula (3)) include four or more groups having an aryl group (the preferred range of other groups is The same as the preferred range of the general formula (1) or general formula (3) described above). Among these forms, the form in which R ³ and R ^{4 in} the general formula (1) (or general formula (3)) are aryl groups is particularly preferable.

The specific form of the “complex insolubilized in the solvent” is not particularly limited, but for example, a form of a lake pigment obtained by lake-forming a specific complex is preferable.
Among the lake pigments, a metal complex compound represented by the following general formula (2) (hereinafter also referred to as “compound represented by the general formula (2)”) or a tautomer thereof is particularly preferable.

~ Compound represented by formula (2) ~
The compound represented by the general formula (2) in the present invention will be described in detail.

  In the general formula (2), A represents a hydrogen atom from any position of the specific complex (the complex represented by the general formula (1) or a tautomer thereof coordinated to a metal or a metal compound). One residue is removed, n represents 2 or 3, and M represents an n-valent metal ion.

The compound represented by the general formula (2) is a lake pigment in which a pyromethene metal complex having a carboxyl group as a substituent is insolubilized with a polyvalent metal ion, that is, insolubilized.
The lake pigment is a colorant having a high concentration, a clear hue and high transparency, and is required to have a thin film / higher sensitivity than a general organic pigment (a pigment other than a lake pigment). This is a particularly preferable colorant form for color filter applications.
Examples of rake formation of a pyromethene metal complex have never been known so far, and it has not been imagined that it can be used particularly suitably for color filter applications.

In the general formula (2), A represents a hydrogen atom from any position of the specific complex (the complex represented by the general formula (1) or a tautomer thereof coordinated to a metal or a metal compound). Represents a residue that has been removed.
A preferable embodiment as a residue obtained by removing one hydrogen atom from an arbitrary position of the specific complex is the same as the preferable embodiment of the specific complex described above except for a difference between a compound and a residue.
The position for removing one hydrogen atom from the specific complex is preferably R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ in the general formula (1).

The A is more preferably a residue obtained by removing one hydrogen atom from any position of the compound represented by the general formula (3).
A preferred embodiment as a residue obtained by removing one hydrogen atom from an arbitrary position of the compound represented by the general formula (3) is the above-described general formula (3) except for the difference between the compound and the residue. ).
The position for removing one hydrogen atom from the compound represented by the general formula (3) is preferably R ² , R ³ , R ⁴ , R ⁵ , R ⁸ or R ⁹ , more preferably R ³ , R ⁴ , R ⁸ or R ⁹ , particularly preferably R ⁸ or R ⁹ .

  In general formula (2), n represents 2 or 3.

In general formula (2), M represents an n-valent metal ion. Examples of metal ions include alkaline earth metal ions (eg, Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ²⁺ ), and transition metal ions (eg, Cu ²⁺ , Zn ²⁺ , Ni ²⁺ , Co ²⁺ , Fe ^2+). , Fe ^{3+ and the} like) and other metal ions (for example, Al ³⁺ ) and the like.
M is preferably an alkaline earth metal ion or a transition metal ion, more preferably Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ²⁺ , Cu ²⁺ , Zn ²⁺ , and particularly preferably Mg ²⁺ , Ca ²⁺ , Ba. ²⁺ , Sr ²⁺ , Zn ²⁺ .

The molar extinction coefficient of the specific colorant (for example, a metal complex compound represented by the general formula (2) or a tautomer thereof) in the present invention is preferably as high as possible from the viewpoint of film thickness.
Specifically, the molar extinction coefficient at the maximum absorption wavelength λmax is preferably 100,000Lmol ^-1 cm ^-1 or more, 150,000Lmol ^-1 cm ^-1 or more is more preferable.
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-3100 (manufactured by Shimadzu Corporation).
The specific colorant in the present invention is preferably a “complex insolubilized in a solvent” from the viewpoint of color purity and transparency, more preferably a lake pigment obtained by lake-forming the specific complex, represented by the general formula (2) The compounds represented or their tautomers are particularly preferred.

  Below, although the representative example of the specific colorant represented by General formula (1) in this invention is shown, this invention is not limited to the following exemplary compound at all. In addition, exemplary compounds (1-1) to (1-6), (2-1) to (2-5), (3-1) to (3-5) and (4-1) to (4-5) ) Is a representative example of the insolubilized metal complex compound (rake compound) represented by the general formula (2), and the exemplary compounds (5) to (7) are insoluble metals represented by the general formula (3). It is also a representative example of complex compounds.

As mentioned above, although the specific colorant in this invention was demonstrated, in the solid dispersion liquid of this invention, a specific colorant may be used individually by 1 type and may use 2 or more types together. In the solid dispersion of the present invention, a specific colorant and other colorants may be used in combination. Examples of other colorants will be described later.
The content of the specific colorant in the total amount of the solid dispersion of the present invention (the total content in the case of 2 or more) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and 10 to 30%. Mass% is particularly preferred.

  The average primary particle diameter of solid particles (specific colorant particles or solid particles containing a specific colorant) in the solid dispersion of the present invention is preferably 10 to 200 nm, more preferably 20 to 150 nm, and more preferably 30 to 150 nm. Is particularly preferred.

<Synthesis method of colorant>
Hereinafter, although the example of the synthesis | combining method of the coloring agent (for example, metal complex compound represented by General formula (2)) in this invention is shown, this invention is not limited to these. The dipyrromethene metal complex can be synthesized in the same manner by selecting a raw material compound with reference to, for example, the synthesis method described in JP-A-2008-292970.

(Synthesis of Exemplary Compound 1-1)
11.4 g of the following precursor (1) was dissolved in 100 mL of THF, and 20 mL of a saturated calcium chloride aqueous solution was added dropwise at room temperature. THF was distilled off under reduced pressure, 100 mL of water was further added thereto, and the resulting crystals were expanded for 1 hour at room temperature. The precipitated crystals were filtered and washed with warm water to give Example Compound 1-1 as a pink solid. Yield 11.5 g. The absorption spectrum of Example Compound 1-1 in DMF showed a maximum maximum wavelength of 547 nm (room temperature, dilute solution). The molar extinction coefficient at the maximum absorption wavelength (maximum maximum wavelength) was 245,000 Lmol ⁻¹ cm ⁻¹ .
Moreover, the identification of exemplary compound 1-1 was performed based on the following measured values.
Elemental analysis: Theoretical value C63.05%, H8.24%, N4.62%, measured value C63.33%, H8.38%, N4.77%. Atomic absorption analysis: theoretical value Ca 1.72 wt-%, Zn 5.62 wt-%, measured value Ca 1.69 wt-%, Zn 5.66 wt-%.

  Other exemplary compounds can also be synthesized according to the synthesis method of exemplary compound 1-1.

  The lake pigment of the present invention may be post-treated after being made into a lake as described above. Examples of post-treatment methods include, for example, solvent salt milling, salt milling, dry milling, solvent milling, pigment particle control step such as acid pasting, solvent heat treatment, resin, surfactant and dispersant, etc. The surface treatment process by.

It is preferable to perform solvent heat treatment and / or solvent salt milling as a post-treatment.
Examples of the solvent used in the solvent heat treatment include water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, and alcohols such as isopropanol and isobutanol. Examples thereof include solvents, polar aprotic organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone, glacial acetic acid, pyridine, and mixtures thereof. An inorganic or organic acid or base may be further added to the solvents mentioned above. The temperature of the solvent heat treatment varies depending on the desired primary particle size of the pigment, but is preferably 40 to 150 ° C, more preferably 60 to 100 ° C. The treatment time is preferably 30 minutes to 24 hours.
As solvent salt milling, for example, a crude azo pigment, an inorganic salt, and an organic solvent that does not dissolve the crude azo pigment are charged into a kneader and kneaded and ground therein. As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. The amount of the inorganic salt used is preferably 3 to 20 times by mass, more preferably 5 to 15 times by mass with respect to the crude azo pigment. As the organic solvent, a water-soluble organic solvent can be suitably used, and the solvent easily evaporates due to a temperature rise during kneading, so that a high boiling point solvent is preferable from the viewpoint of safety. Examples of such organic solvents include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diethylene glycol Propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene Glycol or mixtures thereof. The amount of the water-soluble organic solvent used is preferably 0.1 to 5 times by mass with respect to the lake pigment. The kneading temperature is preferably 20 to 130 ° C, particularly preferably 40 to 110 ° C. As a kneader, for example, a kneader or a mix muller can be used.

<Solvent>
The solid dispersion of the present invention contains a solvent.
As the solvent, any solvent that does not dissolve the colorant (specific colorant) of the present invention can be used without particular limitation. For example, at least one selected from the solvents listed below can be used. it can.

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. Oxyacetic acid alkyl esters (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate). )), 3-oxypropionic acid alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate and the like (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, 3-ethoxy Ethyl propionate, etc.)), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (specifically, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), 2-oxy-2-methylpropionic acid Methyl, ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate , Methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

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

  Moreover, as a solvent in a solid dispersion, what was illustrated as a solvent used by the post-processing after the above-mentioned lake formation may be used.

These solvents may be used alone or in a combination of two or more.
Particularly preferred as a mixed solvent is 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. It is a mixed solvent composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  The total content of the solvent in the solid dispersion is preferably such that the total solid concentration in the solid dispersion is 5 to 50% by mass, more preferably 10 to 40% by mass, and 10 to 30% by mass. % Is particularly preferred.

<Other ingredients>
If necessary, the solid dispersion of the present invention may contain other components (such as various known additives such as surfactants, antioxidants, pH adjusters, and aggregation inhibitors).
However, from the viewpoint of reducing the thickness of the formed colored film, the content of other components is preferably 10% by mass or less based on the total solid content of the solid dispersion.

  Furthermore, in order to improve the dispersibility of the solid dispersion, a dispersant may be used in combination. The colorant represented by the general formula (1) to (3) is dispersed in a non-aqueous vehicle, and the resin used in the non-aqueous vehicle is, for example, petroleum resin, casein, shellac, rosin modified Maleic acid resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber, phenolic resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, Vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluororesin, drying oil, synthetic drying oil, styrene / maleic acid resin, styrene / acrylic resin, polyamide resin , Polyimide resin, benzoguanamine resin, melamine resin, urea Fat chlorinated polypropylene, butyral resin, and vinylidene chloride resin. A photocurable resin may be used as the non-aqueous vehicle. However, from the viewpoint of reducing the thickness of the formed colored film, the smaller the total solid content of the solid dispersion, the better. It is preferably 30% by mass or less, and preferably 20% by mass or less. It is particularly preferable that the content is not more than mass%.

≪Colored photosensitive composition≫
The colored photosensitive composition of the present invention contains the solid dispersion of the present invention described above.
For this reason, according to the colored photosensitive composition of the present invention, a colored pattern having excellent color purity and excellent fastness can be formed. Moreover, the colored photosensitive composition of this invention is excellent also in storage stability.
Furthermore, according to the colored photosensitive composition of the present invention, the color transfer to the adjacent layer or the laminated layer of the formed colored pattern is suppressed, and the solvent resistance and alkali resistance of the colored pattern are improved. .

Further, as described above, the solid dispersion of the present invention can reduce the content of the dispersant (for example, the content in the total solid content can be 10% by mass or less). Even in a colored photosensitive composition containing a solid dispersion, the content of the dispersant can be reduced (for example, the content in the total solid content can be 10% by mass or less). Thereby, the following effects are acquired.
(1) By reducing the content of the dispersant, the content of components other than the colorant can be relatively reduced, and as a result, the color pattern to be formed can be thinned while maintaining a high color density. It can be made.
(2) The content of components (radiation sensitive compounds, polymerizable compounds, binders, etc.) that contribute to photolithographic properties can be relatively increased by decreasing the content of the dispersant. Pattern formability is improved.

The colored photosensitive composition of the present invention may be either positive type or negative type, and preferably further contains a radiation sensitive compound or a polymerizable compound (for example, a polymerizable monomer). Moreover, it can generally comprise using a solvent, and it can comprise further using other components, such as a binder and a crosslinking agent, as needed.
Hereinafter, each component of the colored photosensitive composition of the present invention will be described.

<Solid dispersion>
The solid dispersion contained in the colored photosensitive composition of the present invention is as described above in the section “Solid dispersion”, and the preferred range is also the same.
10-70 mass% is preferable, as for content of the solid dispersion liquid in the whole quantity of the coloring photosensitive composition of this invention, 10-60 mass% is more preferable, and 20-60 mass% is especially preferable.

  The content of the specific colorant in the total solid content of the colored photosensitive composition of the present invention (the total content in the case of two or more) varies depending on the molecular weight and molar extinction coefficient of the colorant, but is 0.5. -80 mass% is preferable, 0.5-70 mass% is more preferable, 1-70 mass% is especially preferable.

<Polymerizable compound>
The colored photosensitive composition of this invention can be comprised suitably by containing at least 1 type of a polymeric compound. The polymerizable compound is mainly contained when the colored photosensitive composition is configured as a negative type.
In addition, a polymeric compound can be contained with the below-mentioned photoinitiator in the positive type | system | group containing a below-mentioned naphthoquinone diazide compound, and can further promote the hardening degree of the pattern formed in this case. Hereinafter, the polymerizable compound will be described.

  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 any of chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or a mixture thereof and a (co) polymer 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. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl 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 paragraph No. 0095 to paragraph No. 0108 of JP-A-2009-288705 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 (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane acrylates as described in JP-B-37193, polyester acrylates and epoxy resins described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490 Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with (meth) acrylic acid, and mixtures thereof.

  Further, compounds having a boiling point of 100 ° C. or higher under normal pressure and having at least one addition-polymerizable ethylenically unsaturated group are disclosed in paragraphs [0254] to [0257] of JP-A-2008-292970. The compounds described are also suitable.

  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 formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R and T present in one molecule may be the same or different.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraph Nos. 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

  The content of the polymerizable compound in the colored photosensitive composition of the present invention is preferably 0.1% by mass to 90% by mass, and 1.0% by mass to 80% by mass with respect to the solid content in the colored photosensitive composition. % By mass is more preferable, and 2.0% by mass to 70% by mass is particularly preferable.

  In the colored photosensitive composition of the present invention, the content ratio of the specific colorant and the polymerizable monomer (compound represented by the general formula (1): polymerizable monomer) is from 1: 2 to the viewpoint of thinning. It is preferably 20: 1, more preferably 1: 1 to 10: 1.

<Radiation sensitive compounds>
The colored photosensitive composition of this invention can be comprised suitably by containing at least 1 type of a radiation sensitive compound.
The radiation-sensitive compound is preferably a compound capable of causing a chemical reaction such as radical generation, acid generation, and base generation with respect to UV light of 400 nm or less. As a result, for example, the binder is insolubilized by reaction such as crosslinking, polymerization, decomposition of acidic groups, polymerization of polymerizable monomers and oligomers coexisting in the coating, crosslinking of the crosslinking agent, etc. It can be insolubilized in the developer.

  When the colored photosensitive composition of the present invention is configured as a negative type, it is preferable to contain a photopolymerization initiator as the radiation-sensitive compound, and the colored photosensitive composition of the present invention is a positive type. When constituted, it is preferable to contain a naphthoquinonediazide compound as the radiation-sensitive compound.

(Photopolymerization initiator)
The photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable monomer to be described later, but is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
The photopolymerization initiator may be further added to the positive colored photosensitive composition containing the naphthoquinone diazide compound, and in this case, the degree of pattern curing to be formed can be further promoted.
Examples of these photopolymerization initiators and naphthoquinone diazide compounds include the compounds described in paragraphs [0260] to [0271] of JP-A-2008-292970.

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. Examples thereof include compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A No. 2004-295116.
Among these, as the polymerization initiator, an oxime compound (also referred to as “oxime photopolymerization initiator” in the present invention) is preferable from the viewpoint of rapid polymerization reaction.

The oxime photopolymerization initiator is not particularly limited. For example, JP 2000-80068 A (paragraph numbers 0004-0296), WO 02/100903 A1, JP 2001-233842 A, and JP 2006-342166 A. Examples thereof include oxime compounds described in the publication (paragraph numbers 0004 to 0264).
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 (manufactured by Ciba Specialty Chemicals).

  Moreover, as said polymerization initiator, the oxime type photoinitiator represented by the following general formula (OX-1) described in Unexamined-Japanese-Patent No. 2007-26979 (paragraph numbers 0016-0082) is also preferable.

[In formula (OX-1), R ^{1 ′} represents a substituent containing an aromatic ring or a heteroaromatic ring. R ^la is an alkyl group having at least one substituent selected from the following group (A). R ^2a is an alkanoyl group, alkenoyl group, aryloyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, heteroaryloxycarbonyl group, alkylthiocarbonyl group, arylthiocarbonyl group, heterocyclic thiocarbonyl group, hetero An arylthiocarbonyl group, -CO-CO-Rd (Rd represents an aromatic ring or a heteroaromatic ring which may have a substituent). n shows the integer of 1-6. ]
<(A) group>
Cyano group, alkenyl group, alkynyl group, -NArAr ', -SAr, -COOH, -CONRaRb, -NRa-CO-Rb, -O-CO-NRaRb, -NRa-CO-ORb, -NRa-CO-NRaRb, _{-SO-Rc, -SO 2 -Rc,} -O-SO 2 -Rc, -SO 2 -NRaRb, -NRa-SO 2 -Ra, -CO-NRa-CORb, -CO-NRa-SO 2 -Rb, _{-SO 2 -NRa-CO-Rb,} -SO 2 -NRa-SO 2 -Rc, -Si (Ra) l (ORb) m, and heterocyclic groups. Here, Ar and Ar ′ independently represent an aromatic ring or a heteroaromatic ring which may have a substituent, and Ra and Rb independently represent a hydrogen atom or an optionally substituted alkyl group, aromatic Rc represents a ring or a heteroaromatic ring, Rc represents an alkyl group, an aromatic ring or a heteroaromatic ring which may have a substituent, l and m each represent an integer of 0 to 3, and l + m = 3 Fulfill.

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

  In the general formula (OX-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 coloration due to heat aging, An alkylene group substituted with an alkenyl group (for example, vinyl group, allyl group), an aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) A substituted alkylene group 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 is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have an amino group and an amino group which may have a substituent are preferable.
In general formula (OX-2), n is preferably an integer of 1 to 2.

  Hereinafter, although the specific example of a compound represented by general formula (OX-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 are used for the colored photosensitive composition of the present invention. Also good.

  When the colored photosensitive composition is a negative type, the content of the photopolymerization initiator in the colored photosensitive composition is preferably 0.01 to 50% by mass with respect to the solid content of the polymerizable compound. 30 mass% is more preferable, and 1-20 mass% is especially preferable. When the content is within the above range, the polymerization proceeds well and good film strength can be obtained.

(Naphthoquinonediazide compound)
Next, the naphthoquinone diazide compound that can be contained when the colored photosensitive composition of the present invention is a positive type will be described.
The naphthoquinonediazide compound is a compound having at least one o-quinonediazide group. For example, o-naphthoquinonediazide-5-sulfonic acid ester, o-naphthoquinonediazide-5-sulfonic acid amide, o-naphthoquinonediazide-4- Examples thereof include sulfonic acid esters and o-naphthoquinonediazide-4-sulfonic acid amide. These ester and amide compounds can be produced by a known method using, for example, the phenol compound described in the general formula (I) in JP-A-2-84650 and JP-A-3-49437. .

  When the colored photosensitive composition is positive, the content of the naphthoquinone diazide compound in the colored photosensitive composition is preferably 2% by mass to 50% by mass, and preferably 2% by mass to 30% by mass. Is more preferable.

<Binder>
The colored photosensitive composition of the present invention preferably contains at least one 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 high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.
Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful. Moreover, as a linear organic high molecular polymer, the polymer as described in paragraph number [0227]-[0234] paragraph of Unexamined-Japanese-Patent No. 2008-292970 is mentioned.

  In addition to the above, the alkali-soluble binder in the present invention includes a polymer having a hydroxyl group added with an acid anhydride, a polyhydroxystyrene resin, a polysiloxane resin, poly (2-hydroxyethyl (meth)), and the like. Acrylate), polyvinylpyrrolidone, 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 polymer containing the above-described polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, 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 general formula (E-1) (hereinafter sometimes referred to as “ether dimer”).

In formula (E-1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

When the colored photosensitive composition of the present invention contains the polymer (a), the heat resistance and transparency of a cured coating film formed using the composition are further improved.
In the general formula (E-1) 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, For example, straight chain such as methyl 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. Or branched alkyl group; aryl group such as phenyl group; cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group , An alicyclic group such as 1-methoxyethyl group, 1-ethoxyethyl group, etc., an alkyl group substituted by alkoxy; substituted by an aryl group such as benzyl group Alkyl 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.

(Alkali-soluble phenol resin)
Moreover, as a binder in this invention, an alkali-soluble phenol resin can also be used. The alkali-soluble phenol resin can be suitably used when the colored photosensitive composition of the present invention is a positive composition. Examples of the alkali-soluble phenol resin include novolak resins and vinyl polymers.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.

  Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin.

  The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

The binder in the present invention described above is preferably a polymer having a mass average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ . A polymer of 5000-5 × 10 ⁴ is particularly preferred.
Moreover, as an acid value of an alkali-soluble binder, 50-300 mgKOH / g is preferable, 75-200 mgKOH / g is more preferable, 80-160 mgKOH / g is especially preferable. When the acid value is within this range, the development residue is less likely to remain during pattern formation, and the coating uniformity is further improved.
The amount of the binder used in the colored photosensitive composition of the present invention is preferably 10% by mass to 90% by mass, and 20% by mass to 80% by mass with respect to the total solid content of the colored photosensitive composition of the present invention. Is more preferable, and 30% by mass to 70% by mass is particularly preferable.

<Crosslinking agent>
By containing the solid dispersion of the present invention, the colored photosensitive composition of the present invention is superior in color purity, has a high extinction coefficient that can be reduced to a thin layer, and is robust. Although it can be excellent, it is also possible to obtain a more highly cured film by additionally using a crosslinking agent.

  The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least one selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. A melamine compound substituted with one group, a guanamine compound, a glycoluril compound, or a urea compound, (c) a phenol compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group, naphthol A compound, or a hydroxyanthracene compound. Of these, polyfunctional epoxy resins are preferred.

  The (a) epoxy resin may be any epoxy resin as long as it has an epoxy group and crosslinkability. For example, bisphenol A glycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol Diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diglycidyl phthalate ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, trimethylolphenol triglycidyl Trivalent glycidyl group-containing low molecular weight compounds typified by ether, TrisP-PA triglycidyl ether, pentaerythritol tetraglycidyl ether, tetramethylol bisphenol Tetravalent glycidyl group-containing low molecular weight compounds typified by tetra-A-glycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

  The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 in the case of melamine compounds, in the case of glycoluril compounds, guanamine compounds, and urea compounds. Although it is 2-4, Preferably it is 5-6 in the case of a melamine compound, and 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.

  Hereinafter, the melamine compound, guanamine compound, glycoluril compound and urea compound of (b) are collectively referred to as a compound (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) according to (b). There is.

  The methylol group-containing compound according to (b) can be obtained by heating the alkoxymethyl group-containing compound according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound according to (b) can be obtained by mixing and stirring the methylol group-containing compound according to (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound according to (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolguanamine, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxymethylguanamine, tetramethylol. Examples thereof include compounds in which 1 to 3 methylol groups of guanamine are acyloxymethylated or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds obtained by acylating 1 to 3 or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
The compounds according to (b) may be used alone or in combination.

The crosslinking agent (c), that is, a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b). As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased.
Hereinafter, these compounds may be collectively referred to as a compound according to (c) (a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl group-containing compound).

  The number of methylol groups, acyloxymethyl groups, and alkoxymethyl groups contained in the cross-linking agent (c) is at least two per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3rd or 5th position of the phenolic compound serving as the skeleton may be unsubstituted or may have a substituent. In addition, the naphthol compound as a skeleton may be unsubstituted or may have a substituent other than the ortho position of the OH group.

The methylol group-containing compound according to (c) is a compound in which the ortho-position or para-position (2-position or 4-position) of the phenolic OH group is a hydrogen atom, and this is used as sodium hydroxide, potassium hydroxide, It can be obtained by reacting with formalin in the presence of a basic catalyst such as ammonia or tetraalkylammonium hydroxide.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeletal compound in the crosslinking agent (c) include a phenol compound, a naphthol compound, a hydroxyanthracene compound, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. For example, phenol, cresol isomers, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4′-bishydroxybiphenyl, TrisP-PA (Honshu Chemical) Kogyo Co., Ltd.), naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, and the like are used.

  Specific examples of the crosslinking agent (c) include trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, trimethylol-3-cresol, tri ( Methoxymethyl) -3-cresol, a compound obtained by methoxymethylating one or two methylol groups of trimethylol-3-cresol, dimethylolcresol such as 2,6-dimethylol-4-cresol, tetramethylolbisphenol A, tetra Methoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethoxymethyl-4,4′-bishydroxybiphenyl, Tr Hexamethylol of sP-PA, hexamethoxymethyl of Tris P-PA, compounds in which 1 to 5 methylol groups have been methoxymethylated hexamethylol of Tris P-PA, Bis-hydroxymethyl naphthalene diol.

Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene.
Examples of the acyloxymethyl group-containing compound include compounds obtained by partially or fully acyloxymethylating the methylol group of the methylol group-containing compound.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

When the coloring photosensitive composition of this invention contains a crosslinking agent, 1-70 mass% is preferable with respect to the total solid (mass) of this composition, and 5-50 mass% is preferable. More preferably, 7-30 mass% is especially preferable.
When the content is within the above range, it is possible to maintain a sufficient degree of cure and elution of the uncured part, and prevent the degree of cure of the cured part from being insufficient or the elution of the uncured part from being significantly reduced. be able to.

<Solvent>
In preparing the colored photosensitive composition of the present invention, a solvent can generally be contained.
The solvent in the colored photosensitive composition of the present invention is not particularly limited as long as it does not dissolve the colorant (specific colorant) of the present invention.
The solvent is not particularly limited as long as it satisfies the solubility of each component of the composition and the applicability of the colored photosensitive composition. Are preferably selected.

Examples of the solvent include the solvents used in the above-described post-treatment after rake formation and those exemplified as the solvent in the solid dispersion. Moreover, you may use the solvent as described in paragraph number [0272] of Unexamined-Japanese-Patent No. 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 Tall acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are more preferable.
These solvents may be used singly or in combination of two or more from the viewpoint of dispersion stability of the solid dispersion, solubility of the UV absorber and alkali-soluble resin, improvement of the coating surface condition, and the like. preferable.
The content of the solvent in the colored photosensitive composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of applicability. 10-50 mass% is especially preferable.

<Other colorants>
The colored photosensitive composition of the present invention may contain other colorants other than the specific colorant described above.
When the colored photosensitive composition of the present invention contains other colorant, the colored photosensitive composition may be prepared by incorporating it into the solid dispersion of the present invention described above, or the solid dispersion of the present invention. Apart from the liquid, a dispersion or solution of other colorant may be prepared, and the resulting dispersion or solution and the solid dispersion of the present invention may be mixed to prepare a colored photosensitive composition. .
Other colorants are not particularly limited, and may be dyes or pigments, and known dyes that have been conventionally used for color filter applications 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.

As other colorants that can be used in combination with the specific colorant, phthalocyanine pigments are preferable from the viewpoint of the color purity of the formed color pattern (color filter).
The phthalocyanine pigment is not particularly limited as long as it is a pigment having a phthalocyanine skeleton. The central metal contained in the phthalocyanine pigment is not particularly limited as long as it is a metal that can form a phthalocyanine skeleton. Among these, magnesium, titanium, iron, cobalt, nickel, copper, zinc, and aluminum are preferably used as the central metal.

  Specific examples of the phthalocyanine pigment in the invention include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 5, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 75, C.I. I. Pigment blue 79, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37, chloroaluminum phthalocyanine, hydroxyaluminum phthalocyanine, aluminum phthalocyanine oxide, and zinc phthalocyanine. Among these, from the viewpoint of light resistance and coloring power, C.I. I. Pigment blue 15, C.I. I. Pigment Blue 15: 6, Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2 is preferable. I. Pigment Blue 15: 6 is preferable.

  When the colored photosensitive composition of the present invention contains a phthalocyanine pigment, the content thereof is preferably 10% by mass to 60% by mass, more preferably 20% by mass to the total solid content component of the colored photosensitive composition. 60 mass% is more preferable, and 35 mass%-50 mass% is the most preferable.

<Polymerization inhibitor>
In the colored photosensitive 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 photosensitive 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.

<Surfactant>
Various surfactants may be added to the colored photosensitive composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
In particular, by containing a fluorosurfactant, the liquid properties (particularly fluidity) when used as a coating liquid can be further improved, and the uniformity of coating thickness and liquid saving can be further improved.
That is, in a colored photosensitive composition containing a fluorosurfactant, the wettability to the coated surface is improved by lowering the interfacial tension between the coated surface and the coating liquid, and coating onto the coated surface is performed. Improves. 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. When the fluorine content is within this range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F554, F780, F781 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, K393, KH-40 (manufactured by Asahi Glass Co., Ltd.), Solsperse 20000 (manufactured by GENECA), etc. Is mentioned.

Specific examples of the cationic surfactant include a phthalocyanine derivative (commercially available product EFKA-745 (manufactured by Morishita Sangyo)), organosiloxane polymer KP341 (manufactured by Shin-Etsu Silicone), (meth) acrylic acid (co) heavy. Combined polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate. Stearate, sorbitan fatty acid ester (pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, manufactured by BASF, Tetronic 304, 701, 704, 901, 904, 150R1, etc. are mentioned.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.
Examples of the silicone-based surfactant include “Toray Silicone DC3PA”, “Same SH7PA”, “Same DC11PA”, “Short SH21PA”, “Short SH28PA”, “Short SH29PA”, “Short SH30PA” manufactured by Torre Silicone Co., Ltd. “Same SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-444 (4) (5) (6) (7) 6” manufactured by Momentive Performance Materials, “TSF-44 60”, “TSF-4452”, “KP341” manufactured by Shin-Etsu Silicone Co., Ltd., “BYK323”, “BYK330” manufactured by Big Chemie, and the like.
Two or more surfactants may be combined.

<Organic carboxylic acid>
Further, when the alkali solubility in the non-exposed area is promoted and the developability of the colored photosensitive composition is further improved, the composition is an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. Is preferably added.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

<Other additives>
Various additives such as fillers, polymer compounds other than those mentioned above, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like may be blended into the colored photosensitive composition as necessary. it can. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
The colored photosensitive composition of the present invention contains a sensitizer and a light stabilizer described in paragraph [0078] of JP-A No. 2004-295116, and a thermal polymerization inhibitor described in paragraph [0081] of the same publication. can do.

<Preparation method of colored photosensitive composition>
The colored photosensitive composition of the present invention can be prepared by mixing the above components.
In the preparation of the colored photosensitive composition of the present invention, the above-described components of the composition may be blended together, or may be sequentially blended 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 Millipore filter having a pore diameter of 0.01 to 3.0 μm, more preferably a pore diameter of about 0.05 to 0.5 μm, and then used. You can also.

The colored photosensitive composition of the present invention is used to color various display devices (for example, liquid crystal display devices (LCD), organic EL display devices, etc.) and color filters used for solid-state imaging devices (for example, CCD, CMOS, etc.). It can be suitably used for pixel formation. In particular, it can be suitably used for forming colored pixels for solid-state imaging devices such as CCDs and CMOSs.
The colored photosensitive composition of the present invention is used for a solid-state imaging device in which a colored pattern is formed in a thin film with a minute size as compared with an existing pigment-based colored photosensitive composition and a good rectangular cross-sectional profile is required. It is particularly suitable for forming a color filter. In addition, the colored photosensitive composition of the present invention is advantageous in terms of color transfer as compared with a system using a conventionally proposed dye, and can form a color filter for a solid-state imaging device having a small pixel size. Particularly preferred.

  In general, 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 the colorant increases, Furthermore, because the hue is blue, the line width sensitivity is deteriorated and the DOF margin is narrowed. As a result, the pattern formability is easily impaired. This is particularly noticeable when the pixel pattern size is 1.0 to 1.7 μm (further 1.2 to 1.5 μm). In addition, in the case of a thin film having a thickness of 1 μm or less, the amount of components that contribute to photolithographic properties excluding the colorant in the film is relatively reduced, and the amount of other components is further reduced by the increase in the amount of colorant. Sensitivity is increased and the pattern is easily peeled off in the low exposure area. In this case, heat sagging is likely to occur when heat treatment such as post-baking is performed. These are particularly remarkable when the film thickness is 0.005 μm to 0.9 μm (further 0.1 μm to 0.7 μm).

  However, if the colored photosensitive composition of the present invention is used, a color filter having an excellent cross-sectional profile can be produced even with the pixel pattern size of 2 μm or less as described above.

  Further, in general, in a curable composition using a dye, the dye is likely to soak into the previously formed pattern (or layer) of another color at the time of coating (color soaking at the time of the next color coating). Furthermore, a curable composition using a dye requires the addition of a large amount of dye, and as a result, the relative content of components that contribute to photolithographic properties is reduced. For this reason, the pattern is likely to be peeled off in a low exposure area due to a decrease in sensitivity, or a desired shape and color density cannot be obtained due to elution of dye during alkali development, etc. Dye elution). Furthermore, in a curable composition using a dye, when heat treatment is performed after film formation, color transfer is likely to occur between adjacent pixels or between layers in a stacked state (thermal diffusion by heat treatment).

  However, if the colored photosensitive composition of the present invention is used, while maintaining the transparency of the dye, the above-mentioned dye-specific dye soaks in the next color coating, dye elution in alkali development, heat treatment A color filter in which thermal diffusion (color transfer) can be significantly suppressed can be produced.

≪Inkjet ink≫
The ink-jet ink of the present invention contains the solid dispersion of the present invention described above.
For this reason, according to the inkjet ink of the present invention, it is possible to form a colored image (for example, a colored pixel) excellent in color purity and fastness.
Moreover, the inkjet ink of the present invention is excellent in storage stability.
Furthermore, the ink-jet ink of the present invention is less susceptible to ejection disturbance such as flying bend and non-ejection during continuous and intermittent ejection, has excellent ejection stability, and recoverability after a certain period of rest. Excellent recoverability when non-ejection occurs.
The ink-jet ink of the present invention is particularly preferably used for producing a color filter by an ink-jet method.

<Solid dispersion>
The solid dispersion contained in the ink-jet ink of the present invention is as described in the above section “Solid dispersion”, and the preferred range is also the same.
The content of the specific colorant in the inkjet ink of the present invention (the total content in the case of two or more) is preferably 1 to 20% by mass, more preferably 5 to 15% by mass, based on the total amount of the ink. . If the content is 1% by mass or more, the film thickness for achieving the optical density required for the color filter can be made thinner, so that the black matrix can also be made thinner and the black matrix can be formed more easily. It becomes.
If the content is 20% by mass or less, an increase in ink viscosity can be further suppressed, discharge properties can be further improved, and dispersion in a solvent can be facilitated.

<Solvent>
The inkjet ink of the present invention contains a solvent.
The solvent in the inkjet ink of the present invention is a solvent that does not dissolve the colorant (specific colorant) of the present invention, and is basic as long as the solubility of each component other than the colorant and the boiling point described later are satisfied. Although not particularly limited, it is preferably selected in consideration of the solubility, coating property and safety of the binder described below. Examples of the solvent include the solvents described in paragraph numbers [0030] to [0040] of JP-A-2009-13206.
Moreover, as a solvent in the ink for inkjet of this invention, the solvent demonstrated as a solvent in the colored photosensitive composition of this invention can also be used.

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

  The ink-jet ink of the present invention preferably contains a solvent having a high boiling point among the solvents described above, from the viewpoints of ink discharge performance with respect to the nozzle and wettability with respect to the substrate.

The boiling point of the solvent used in the present invention is preferably 130 to 280 ° C.
If the boiling point of the solvent is 130 ° C. or more, the uniformity of the shape of the pixels in the plane is further improved.
If the boiling point of a solvent is 280 degrees C or less, the solvent removability by prebaking will improve more.
The boiling point of the solvent means a boiling point under a pressure of 1 atm, and can be known from a property value table such as a compound dictionary (Chapman & Hall). These may be used alone or in combination of two or more.

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

<Polymerizable compound>
The inkjet ink of the present invention may contain a polymerizable compound.
Addition of the polymerizable compound improves the adhesion between the ink droplet and the substrate.
In addition, it can be expected to improve the dispersion uniformity of the above-mentioned specific colorant in the ink and to improve the fastness such as weather resistance and heat resistance.
The polymerizable compound is preferably a polymerizable monomer, and the polymerizable monomer is not particularly limited. However, there are many variations of various substituents, and (meth) acrylic monomers and epoxy monomers are easily available. And at least one selected from oxetanyl monomers.

  As the polymerizable monomer, a monomer having two or more polymerizable groups (hereinafter also referred to as “bifunctional or higher functional monomer”) is preferable. The polymerizable monomer is not particularly limited as long as it can be polymerized by active energy rays and / or heat, but it has three or more polymerizable groups from the viewpoint of film strength and solvent resistance. (Hereinafter also referred to as “tri- or higher functional monomer”) is more preferable.

Although there is no restriction | limiting in particular as a kind of polymeric group mentioned above, As above-mentioned, an acryloyloxy group, a methacryloyloxy group, an epoxy group, and an oxetanyl group are especially preferable. Examples of the polymerizable monomer include compounds described in paragraph numbers [0054] to [0068] of JP-A-2009-13206.
In addition, as the polymerizable compound in the inkjet ink of the present invention, the polymerizable compounds described as the polymerizable compound in the colored photosensitive composition of the present invention can also be used.

  The content of the polymerizable compound described above is preferably 30 to 80% by mass, and more preferably 40 to 80% by mass in the solid content of the ink jet ink. If the content of the polymerizable compound 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 inkjet ink for specifying the blending ratio includes all components except the solvent, and a liquid polymerizable compound is also included in the solid content.

<Binder resin>
The ink jet ink of the present invention may contain a binder resin for the purpose of adjusting the viscosity and adjusting the ink hardness. As the binder resin, a binder resin that is simply dried and solidified such that it is composed only of a resin that does not have polymerization reactivity may be used. However, in order to impart sufficient strength, durability, and adhesion to the coating film, a binder resin that can cure the pixel by a polymerization reaction after forming a pixel pattern on the substrate by an inkjet method is used. Preferably, it can be polymerized and cured, such as a photo-curable binder resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, etc., or a thermosetting binder resin that can be polymerized and cured by heating. Binder resin can be used.
Moreover, what was demonstrated as a binder in the colored photosensitive composition of this invention can also be used as binder resin in the inkjet ink of this invention.

<Polymerization initiator>
The inkjet ink of the present invention may be used in combination with a polymerization initiator for the purpose of promoting the polymerization reaction of the polymerizable compound and the binder resin. The polymerization initiator can be selected according to the type of polymerizable monomer and binder used in the ink jet ink and the polymerization route.
Moreover, what was demonstrated as a photoinitiator in the colored photosensitive composition of this invention can also be used as a polymerization initiator in the inkjet ink of this invention.

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

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

  Examples of other additives include other additives described in paragraph numbers [0058] to [0071] of JP-A No. 2000-310706.

  As content of each component of the inkjet ink of this invention, 1-20 mass% is preferable, and, as for the total content of the solid dispersion of the above-mentioned specific colorant, 5-15 mass% is more preferable, Content of a solvent Is preferably 30 to 90 mass%, more preferably 50 to 85 mass%, the content of the polymerizable compound is preferably 5 to 50 mass%, more preferably 7 to 30 mass%, and the surfactant content is 0. .1 to 5% by mass is preferable.

<Inkjet ink manufacturing method>
For the production of the inkjet ink of the present invention, a known inkjet ink production method can be applied. For example, after the above-mentioned specific colorant is dispersed in a solvent, each component necessary for the ink-jet ink (for example, a polymerizable monomer and a binder) can be dissolved to prepare the ink-jet ink.

  When preparing the monomer liquid, if the solubility of the material used in the solvent is low, the monomer liquid may be appropriately subjected to a treatment such as heating or ultrasonic treatment within a range that does not cause a polymerization reaction. Is possible.

  When the above-mentioned specific colorant is dispersed in an aqueous medium, the specific colorant and oil are used as disclosed in JP-A-11-286637, JP-A-2001-240763, JP-A-2001-262039, JP-A-2001-247788. A specific colorant in which colored fine particles containing a soluble polymer are dispersed in an aqueous medium, or dispersed in a high-boiling organic solvent as in JP-A Nos. 2001-262018, 2001-240763, and 2001-335734 May be dispersed in an aqueous medium. Specific methods for dispersing the above-mentioned specific colorant in an aqueous medium, oil-soluble polymers to be used, high-boiling organic solvents, additives, and amounts used thereof are preferably those described in the above-mentioned patent documents. be able to. Or you may disperse | distribute the above-mentioned specific colorant to a fine particle state with solid. At the time of dispersion, a dispersant or a surfactant can be used.

  Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patent documents, JP-A-5-148436, 5-295212, 7-97541, 7-82515, 7-185858, Details are described in Japanese Laid-Open Patent Publication Nos. 11-286637 and 2001-271003, and can also be used for preparing the ink-jet ink of the present invention.

<Physical properties of ink-jet ink>
The physical property value of the inkjet ink of the present invention is not particularly limited as long as it can be ejected by the inkjet head, but the viscosity at the time of ejection is preferably 2 to 30 mPa · s from the viewpoint of stable ejection. 20 mPa · s is more preferable. Moreover, when ejecting with an apparatus, it is preferable to maintain the temperature of the inkjet ink at a substantially constant temperature in the range of 20 to 80 ° C. Thereby, the fall of an ink viscosity can be suppressed more and nozzle clogging can be suppressed more.

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

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

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

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

≪Color filter and manufacturing method≫
The color filter of the present invention is formed by using the colored photosensitive composition of the present invention or the inkjet ink of the present invention. For this reason, the color filter of this invention is excellent in color purity and fastness.

Next, a method for producing a color filter using the colored photosensitive composition of the present invention (a method for producing a color filter of the present invention) will be described.
Examples of a method for forming a pattern by the photolithography method using the colored photosensitive composition of the present invention include the methods described in paragraphs [0277] to [0284] of JP-A-2008-292970.

  Specifically, a step of coating the colored photosensitive composition on a support to form a colored layer (hereinafter also referred to as “colored layer forming step”), and exposing the formed colored layer through a mask And a step of developing a color pattern by developing the exposed colored layer (hereinafter also referred to as “development step”). It is done.

<Colored layer forming step>
In the method for producing a color filter of the present invention, first, the above-described colored photosensitive composition of the present invention is applied onto a support by a coating method such as spin coating, cast coating, roll coating, and the coating layer is formed. Then, if necessary, preliminary curing (pre-baking) is performed, and the coating layer is dried to form a colored layer (colored layer forming step).

  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.

  In addition, when the colored photosensitive composition is spin-coated on the support, in order to reduce the dripping amount of the liquid, before dropping the colored photosensitive composition, an appropriate organic solvent is dropped and rotated, The familiarity of the colored photosensitive composition with the support can be improved.

Examples of the prebaking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
The thickness of the colored layer formed from the colored photosensitive composition is appropriately selected according to the purpose, but is generally preferably 0.2 μm to 5.0 μm, preferably 0.3 μm to 2 More preferably, it is 0.5 μm, most preferably 0.3 μm to 1.5 μm. In addition, the thickness of the colored layer here is a film thickness after pre-baking.

<Exposure process>
Then, in the manufacturing method of the color filter of this invention, exposure through a mask is performed to the colored layer formed on the support body (exposure process).
As light or radiation applicable to this exposure, g-line, h-line, i-line, KrF light and ArF light are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is ^preferably irradiated at an exposure dose of ^{100mJ / cm 2 ~10000mJ / cm 2} .

  Other exposure rays include ultra high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser light sources, fluorescent lamps, tungsten lamps, solar Light or the like can also be used.

(Exposure process using laser light source)
In the exposure method using the laser light source, an ultraviolet laser can be used as the light source. Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplification and oscillation of light waves, utilizing the phenomenon of stimulated emission that occurs in materials with inversion distribution, crystals, glass, liquids, dyes as excitation media, There are gases and the like, and lasers having an oscillation wavelength for known ultraviolet light such as solid laser, liquid laser, gas laser, and semiconductor laser can be used from these media. Among these, a solid laser and a gas laser are preferable from the viewpoint of laser output and oscillation wavelength.

  As a laser that can be used in the exposure method using the laser light source, an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm is preferable, and an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm is more preferable. , Which is preferable in that it matches the photosensitive wavelength of the resist (colored photosensitive composition).

Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. .
The exposure amount for the object to be exposed (colored ^layer), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm 2 is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

  An exposure apparatus that can be used for the exposure method using the laser light source is not particularly limited, but commercially available devices include Calisto (buoy technology), EGIS (buoy technology), and DF2200G ( Dainippon Screen Co., Ltd. can be used, and devices other than those described above are also preferably used.

  Further, a light emitting diode (LED) and a laser diode (LD) can be used as the active radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has introduced a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit actinic radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. The actinic radiation source particularly preferred in the present invention is a UV-LED, particularly preferably a UV-LED having a peak wavelength at 340 to 370 m.

  Since the parallelism of the ultraviolet laser is good, pattern exposure can be performed without using a mask at the time of exposure. However, it is more preferable to expose the pattern using a mask because the linearity of the pattern is further increased.

The exposed colored layer can be heated at 70 ° C. to 180 ° C. for about 0.5 to 15 minutes using a hot plate or oven before the next development processing.
The exposure can be performed while flowing a nitrogen gas in the chamber in order to suppress oxidation fading of the colorant in the colored layer.

<Development process>
Subsequently, the colored layer after exposure is developed with a developer (development process). Thereby, a negative or positive colored pattern (resist pattern) can be formed.
As long as the developing solution dissolves the uncured portion of the colored layer and does not dissolve the cured portion, a combination of various organic solvents or an alkaline aqueous solution can be used. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 11 to 13, more preferably pH 11.5 to 12.5. In particular, an alkaline aqueous solution prepared by adjusting tetraethylammonium hydroxide so that its concentration is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass can be used as the developer.
The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 23 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.

  Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water. The cleaning method is also appropriately selected according to the purpose. While rotating a support such as a silicon wafer substrate at a rotational speed of 10 rpm to 500 rpm, pure water is supplied from the ejection nozzle in a shower shape from above the rotation center. A rinsing process can be performed.

  Thereafter, if necessary, post-heating and / or post-exposure may be performed on the formed pattern (resist pattern) to accelerate the curing of the pattern (post-curing step).

-UV irradiation process-
In the ultraviolet irradiation step, the colored pattern obtained in the developing step is irradiated with ultraviolet light (UV light) (for example, an irradiation light amount [mJ / cm ² ] that is 10 times or more of the exposure amount [mJ / cm ² ] in the exposure process before development). ² ] UV light (UV light). By providing an ultraviolet irradiation step between the development step and the heat treatment described below, it is possible to effectively prevent color migration when heated later.

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.

The UV light irradiation is preferably performed as an irradiation light amount [mJ / cm ² ] that is 10 times or more of the exposure amount at the time of exposure in the pattern forming step. If the irradiation light quantity in this step is 10 times or less, color transfer between colored pixels and between upper and lower layers can be more effectively suppressed.
Especially, the irradiation light quantity of UV light is preferably 12 times or more and 200 times or less, more preferably 15 times or more and 100 times or less the exposure amount at the time of exposure in the pattern forming step.

In this case, it is preferable that the integrated irradiation illuminance in the irradiated ultraviolet light 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.
The post-heating is preferably performed at 100 ° C. to 300 ° C. using a hot plate or an oven, and more preferably 150 ° C. to 250 ° C. The post-heating time is preferably 30 seconds to 30000 seconds, and more preferably 60 seconds to 1000 seconds.

  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 irradiating with UV light (UV curing), it is preferably performed at a low temperature of 20 ° C. or higher and 50 ° C. or lower (preferably 25 ° C. or higher and 40 ° C. or lower). 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.

  Either post-exposure or post-heating 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 a plurality of hue pixels, the pattern forming step (and the curing step if necessary) is repeated in accordance with the desired number of colors to obtain a color filter configured in a desired number of hues. Can be produced.

Even when the colored photosensitive composition according to the present invention adheres to, for example, a nozzle of a coating apparatus discharge section, a piping section of a coating apparatus, or the inside of a coating apparatus, it can be easily cleaned and removed using a known cleaning liquid. . In this case, in order to perform more efficient cleaning removal, it is preferable to use the solvent contained in the colored photosensitive composition according to the present invention as the cleaning liquid.
JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP 2007-2101 A, JP 2007-2102 A, JP 2007-281523 A and the like are also preferably used as cleaning liquids for cleaning and removing the colored photosensitive composition according to the present invention. it can.
Of the above, alkylene glycol monoalkyl ether carboxylates and alkylene glycol monoalkyl ethers are preferred.
These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. In a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio is particularly preferably 60/40.
In addition, in order to improve the permeability of the cleaning liquid to the colored photosensitive composition, a surfactant related to the present composition described above may be added to the cleaning liquid.

  Furthermore, as a method for producing a color filter, a method using an ink jet method can be mentioned. A method for producing a color filter by an inkjet method is not particularly limited, and a step of preparing a substrate having a recess partitioned by a partition, and applying the inkjet ink droplets to the recess by an inkjet method, And a step of forming colored pixels of the color filter. For example, the methods described in paragraph numbers [0114] to [0128] of JP-A-2008-250188 can be used.

  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 suitable for use in a display device such as a liquid crystal display, an organic EL display, a liquid crystal projector, a game machine, and a mobile terminal such as a mobile phone, a digital camera, and a car navigation system, in particular, a color display device. Applicable.
Further, it can be suitably used as a color filter for a solid-state imaging device such as a CCD image sensor or a CMOS image sensor used in a digital camera, a digital video camera, an endoscope, a mobile phone, or the like. Particularly, it is suitable for a high-resolution CCD element or CMOS element exceeding 1 million pixels.

≪Solid-state imaging device≫
The solid-state imaging device of the present invention includes the color filter of the present invention.
Specifically, a CCD image sensor or a CMOS image sensor used for a digital camera, a digital video camera, an endoscope, a mobile phone, or the like is preferable as the solid-state imaging device of the present invention. Particularly, a high-resolution CCD image sensor or CMOS image sensor exceeding 1 million pixels is suitable.
The configuration of the solid-state imaging device is not particularly limited as long as it includes the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be given.
That is, it has a structure in which a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area is provided on a support, the color filter of the present invention is provided thereon, and then a micro lens is laminated. .

  In addition, the camera system including the color filter of the present invention includes a cover lens, a microlens, and the like in which a camera lens and an IR cut film are dichroically coated, from the viewpoint of light fading of a color material. It is desirable that the characteristics absorb part or all of UV light of 400 nm or less. Further, 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 color material. For example, a part or the whole of the camera system Is preferably sealed with nitrogen gas.

≪Display device≫
The display device of the present invention includes the color filter of the present invention.
Specifically, as a display device of the present invention, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone. Display devices such as digital camera display devices and car navigation display devices, particularly color display devices are suitable.

For the definition of display devices and explanation of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, published by Industrial Research Institute 1990)”, “Display Device (written by Junaki Ibuki, Industrial Books Co., Ltd.) Issue year)).
The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a lateral electric field driving method such as IPS, a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
The color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, as the required characteristics for the color filter layer, in addition to the normal required characteristics, the required characteristics for the interlayer insulating film, that is, low dielectric constant and stripping solution resistance are required. In the color filter of the present invention, it is considered that the transparency of the ultraviolet light that is the exposure light can be increased by using an exposure method using an ultraviolet light laser, or by selecting the hue and film thickness of the colored pixels. . As a result, the curability of the colored pixel is improved, and a pixel free from chipping, peeling, or twisting can be formed. Therefore, the resistance to the peeling liquid of the colored layer provided directly or indirectly on the TFT substrate is improved. Useful for liquid crystal display devices. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
Further, the colored layer formed by the COA method has a rectangular shape with a side length of about 1 to 15 μm in order to connect the ITO electrode arranged on the colored layer and the terminal of the driving substrate below the colored layer. It is necessary to form a conduction path such as a through-hole or a U-shaped depression, and the dimension of the conduction path (that is, the length of one side) is particularly preferably 5 μm or less. It is also possible to form a conduction path of 5 μm or less.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest trends in the market (issued by Toray Research Center Research Division 2001)".

In addition to the color filter of the present invention, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members.
Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., 2003) ”.

  Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.

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

  As described above, various embodiments of the solid dispersion, the colored photosensitive composition, the inkjet ink, the color filter and the production method thereof, the solid-state imaging device, the display device, and the metal complex compound and the tautomer thereof according to the present invention are described. The present invention has been described in detail, but the present invention is not limited to the above-described embodiment, and it is needless to say that various improvements and modifications may be made without departing from the gist 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, unless otherwise specified, “%” and “part” represent “mass%” and “part by mass”, and “wt-%” and “wt%” represent “mass%”. "Molecular weight" represents "weight average molecular weight".

[Example 1]
<Preparation of solid dispersion>
40 parts by weight of Example Compound 1-1 (colorant) (average particle diameter: 270 nm, maximum absorption wavelength: 547 nm), 180 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), bead mill (zirconia beads 0 (3 mm diameter) for 3 hours, and a solid dispersion was prepared.
With respect to the prepared solid dispersion, the average primary particle diameter of the solid fine particles (colorant fine particles) was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 85 nm.
Moreover, the solubility in 25 degreeC with respect to PGMEA of exemplary compound 1-1 was 0.2 mass%.

<C. I. Pigment Blue 15: 6 Preparation of Dispersion>
C. I. Pigment Blue 15: 6 (11.5 parts by mass (average particle size 55 nm)), pigment dispersant BY-161 (manufactured by BYK) (3.5 parts by mass) and PGMEA (85 parts by mass) were mixed with a bead mill (zirconia beads 0). (3 mm diameter) for 3 hours to mix and disperse to prepare a pigment dispersion. Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion. With respect to the pigment dispersion, the average primary particle size of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 25 nm.

<Preparation of colored photosensitive composition>
The following components were mixed to obtain a colored composition 1 which is a colored photosensitive composition.

・ The above-mentioned solid dispersion (solid dispersion of Exemplified Compound 1-1): 37.99 parts I. Pigment Blue 15: 6 dispersion (solid concentration 15%, pigment concentration 11.5%) ... 55.47 parts, polymerizable monomer (KAYARAD DPHA (manufactured by Nippon Kayaku)) ... 3.34 parts, polymerization initiator (CGI) -242 (manufactured by Ciba Specialty Chemicals; oxime polymerization initiator)) ... 0.96 parts resin (benzyl methacrylate / copolymer of methacrylic acid 30% PGMEA solution (resin A) (molar ratio = 70: 30, weight average molecular weight 30000)) 0.53 parts · Fluorosurfactant (Solsperse 20000, manufactured by Zeneca) 1% CyH solution
… 0.1 part

<Production of monochromatic color filter and evaluation of color blur>
(1) Production of glass substrate with undercoat layer A glass substrate (Corning 1737) was heat-treated in an oven at 200 ° C. for 30 minutes. Next, CT-4000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is applied onto this glass substrate so as to have a dry film thickness of 1 μm, and further heated and dried on a hot plate at 200 ° C. for 5 minutes to form an undercoat layer. Then, a glass substrate with an undercoat layer was obtained.

(2) Application, exposure and development of colored photosensitive composition The colored photosensitive composition (colored composition 1) is applied onto the undercoat layer of the glass substrate with an undercoat layer obtained in (1) above, and is photocured. A characteristic coating film was formed. Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.6 μm. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), an exposure dose of 100 mJ / cm in a range of 100 to 2500 mJ / cm ² through a Bayer pattern mask having a pattern of 10.0 μm square at a wavelength of 365 nm. Irradiation was carried out while changing by ² cm ² .
Then, the glass 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 CD-2000 (Fuji Film Electronics Co., Ltd.). Paddle development was performed at 23 ° C. for 60 seconds using Materials Co., Ltd. Next, while rotating the glass substrate at a rotation speed of 50 rpm, pure water was supplied from the upper part of the rotation center in a shower-like manner and rinsed, and then spray-dried to obtain a colored pattern.

(3) Post-curing treatment of colored pattern The obtained colored pattern was irradiated with 350 mW / cm ² at 35 ° C for 30 seconds using a UV irradiation device (UMA-802-HC552FFAL: manufactured by Ushio Electric Co., Ltd.). Then, it heated at 200 degreeC for 300 seconds (post-baking), and the coloring pattern was hardened.
Thus, a glass substrate with a colored pattern (blue monochromatic color filter) was obtained.

(4) Preparation of transparent film composition The components of the following composition were mixed and dissolved to prepare a transparent film composition (CT-1).
Propylene glycol monomethyl ether acetate (PGMEA) 63.0 parts Ethyl ethoxypropionate (EEP) 27.0 parts Resin [benzyl methacrylate / methacrylic acid (molar ratio = 70: 30)]
... 4.88 parts-KAYARAD DPHA (manufactured by Nippon Kayaku, polymerizable compound) ... 4.88 parts-polymerization inhibitor (p-methoxyphenol) ... 0.0001 parts-fluorinated surfactant (F-475, large Nippon Ink Chemical Co., Ltd.) ... 0.01 parts Photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd. 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1 , 2-octadiene)
... 0.23 parts

(5) Application of transparent film composition After applying the transparent film composition CT-1 prepared in the above (4) to the colored pattern forming surface side of the glass substrate with a colored pattern obtained in the above (3), 100 is applied. Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 0 ° C.

(6) Post-curing treatment of transparent film composition Using the UV irradiation apparatus UMA-802-HC552FFAL (made by Ushio Electric Co., Ltd.) on the glass substrate coated with the transparent film composition CT-1 in (5) above, 35 UV light of 350 mW / cm ² was irradiated at 30 ° C. for 30 seconds. Thereafter, the glass substrate on which the irradiated coating film was formed was subjected to heat treatment at 200 ° C. for 300 seconds.
A transparent film was formed on the colored pattern forming surface side of the glass substrate with the colored pattern as described above.

(7) Evaluation Alkali elution resistance, solvent resistance, color transfer due to thermal diffusion, color purity, storage stability, heat resistance, light resistance of a coating film coated on a glass substrate using a colored photosensitive composition Was evaluated as follows. The evaluation results are shown in Table 2 below.

(Alkali elution resistance)
In (2) above, the spectrum (spectrum A) of the coating film after pre-baking and the spectrum (spectrum B) after development at the exposed portion of this coating film are measured, and the dye remaining is determined from the difference between the spectrum A and the spectrum B. The rate (%) was calculated and used as an index for evaluating the resistance to alkali elution. This value indicates that the closer to 100%, the better the alkali elution resistance.

[Solvent resistance]
In the above (3), the spectrum of the colored pattern after post-baking was measured (spectrum A).
The transparent film composition (CT-1) obtained in (4) above was applied to this colored pattern (substrate with colored pattern) so as to have a film thickness of 1 μm and prebaked, and then CD-2000. (Developed by Fuji Film Electronics Materials Co., Ltd.) Using a developer, development was performed under conditions of 23 ° C. and 120 seconds, and spectroscopy was measured again (spectrum B). The dye residual ratio (%) was calculated from the difference between the spectrum A and the spectrum B, and this was used as an index for evaluating the solvent resistance. This value indicates that the closer to 100%, the better the solvent resistance.

[Color transfer by thermal diffusion]
Apply the CT-2000L solution (base clearing agent, manufactured by FUJIFILM Electronics Materials Co., Ltd.) to the colored pattern forming surface of the color filter produced as described in (3) so that the dry film thickness is 1 μm. After drying to form a transparent film, heat treatment was performed at 200 ° C. for 5 minutes. After the heating, the absorbance of the transparent film adjacent to the colored pattern was measured with a microspectrophotometer (LCF-1500M manufactured by Otsuka Electronics Co., Ltd.). The ratio [%] of the absorbance value of the obtained transparent film to the absorbance of the colored pattern similarly measured before heating was calculated and used as an index for evaluating the color transfer.
-Criteria-
Color transfer to adjacent pixels (%)
A: Color transfer to adjacent pixels ≦ 1%
○: 1% <color transfer to adjacent pixels ≦ 10%
Δ: 10% ≦ color transfer to adjacent pixel ≦ 30%
×: Color transfer to adjacent pixels> 30%

[Color purity / transmittance evaluation]
The transmission spectrum of the color filter obtained as described above was measured, and the transmittance at 450 nm was evaluated. The larger the transmittance, the greater the amount of blue light transmitted, indicating that the blue color filter is excellent.
-Criteria-
The transmittance at 450 nm when the transmittance at the maximum absorption wavelength of the color filter was corrected to 2% (normalized) was determined.
○: 450 nm transmittance ≧ 90%
Δ: 80% ≦ 450 nm transmittance <90%
×: 450 nm transmittance <80%

[Storage stability]
The colored photosensitive composition prepared above was stored at room temperature for one month, the degree of precipitation of foreign matters after storage was visually observed, and evaluated according to the following criteria.
-Criteria-
○: No precipitation was observed.
Δ: Slight precipitation was observed.
X: Precipitation was recognized.

〔Heat-resistant〕
The color filter produced as described in (3) above was heated on a hot plate at 260 ° C. for 5 minutes (heat resistance test). With a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.), the color difference (ΔEab value) before and after the heat resistance test was measured and evaluated according to the following evaluation criteria. A smaller ΔEab value indicates better heat resistance.
-Criteria-
○: ΔEab value <5 or less Δ: 5 ≦ ΔEab value ≦ 10
×: 10 <ΔEab value

[Light resistance]
The color filter produced as described in (3) above was irradiated with a xenon lamp at 100,000 lux for 48 hours (equivalent to 4.8 million lux · h) (light resistance test). The color difference (ΔEab value) before and after the light resistance test was measured and evaluated according to the following evaluation criteria. The smaller the ΔEab value, the better the light resistance.
~ Criteria ~
○: ΔEab value <3
Δ: 3 ≦ ΔEab value ≦ 10
×: 10 <ΔEab value

[Examples 2 to 5 and Comparative Examples 1 to 5]
A color filter was prepared in the same manner as in Example 1 except that the colorant (Exemplary Compound 1-1) in Example 1 was changed to the colorant shown in Table 1 having the same mass, and the same as in Example 1. Evaluation was performed.
In addition, in the solid dispersion of Exemplary Compound 1-2, the average primary particle size of the solid fine particles was 80 nm. Moreover, the solubility in 25 degreeC with respect to PGMEA of exemplary compound 1-2 was 0.1 mass%.
Moreover, identification of the exemplary compound 1-2 was performed based on the following measured values.
Elemental analysis: Theoretical value C63.49%, H8.30%, N4.85%, measured value C63.21%, H8.45%, N4.59%. Atomic absorption analysis: theoretical value Mg 1.05 wt-%, Zn 5.67 wt-%, measured value Mg 1.11 wt-%, Zn 5.61 wt-%.

Moreover, in the solid dispersion liquid of exemplary compound 2-1, the average primary particle diameter of the solid fine particles was 85 nm. Moreover, the solubility in 25 degreeC with respect to PGMEA of exemplary compound 2-1 was 0.1 mass%.
Moreover, identification of the exemplary compound 2-1 was performed based on the following measured values.
Elemental analysis: Theoretical value C61.08%, H7.81%, N4.38%, measured value C61.20%, H8.11%, N4.54%. Atomic absorption analysis: theoretical value Ca1.56 wt-%, Zn 5.12 wt-%, measured value Ca1.58 wt-%, Zn 5.21 wt-%.

In addition, in the solid dispersion of Exemplified Compound 2-3, the average primary particle size of the solid fine particles was 70 nm. Moreover, the solubility in 25 degreeC with respect to PGMEA of exemplary compound 2-3 was 0.05 mass%.
Moreover, identification of the exemplary compound 2-3 was performed based on the following measured values.
Elemental analysis: Theoretical value C 58.84%, H 7.52%, N 4.22%, measured value C 58.74%, H 7.71%, N 4.33%. Atomic absorption analysis: theoretical value Ba 5.18 wt-%, Zn 4.93 wt-%, measured value Ba 5.22 wt-%, Zn 4.99 wt-%.

Moreover, in the solid dispersion liquid of exemplary compound 3-3, the average primary particle diameter of the solid fine particles was 68 nm. Moreover, the solubility in 25 degreeC with respect to PGMEA of exemplary compound 3-3 was 0.1 mass%.
Moreover, the identification compound 3-3 was identified based on the following measured values.
Elemental analysis: Theoretical value C63.05%, H8.24%, N4.62%, measured value C63.33%, H8.38%, N4.77%. Atomic absorption analysis: theoretical value Ba 5.49 wt-%, Zn 5.23 wt-%, measured value Ba 5.38 wt-%, Zn 5.19 wt-%.

As can be seen from Table 2 above, Examples 1 to 5 using the solid dispersion of the present invention are superior in alkali elution resistance and solvent resistance as compared with Comparative Examples 1 to 5. It also showed a remarkable effect on color transfer due to thermal diffusion. Further, it can be seen that the solid dispersions of Examples 1 to 5 have good storage stability despite being solid-dispersed. Furthermore, excellent fastness (heat resistance and light resistance) was exhibited as compared with Comparative Examples 1 and 2 in which solid dispersion was not performed.
Thus, the colored photosensitive composition produced using the solid dispersion of the present invention is very suitable for use as a color filter for a solid-state imaging device.
In addition, as shown in Examples 1 to 5 above, the solid dispersion of the present invention can be unexpectedly dispersed alone without using a dispersant, and thinned (with components other than the colorant). It has been found that the present invention is very suitable for recent color filter applications in which the composition ratio is reduced.

  Although the example which forms a blue coloring pattern (blue color filter) on a glass substrate was demonstrated as Examples 1-5 above, the solid-state image sensor substrate (Silicon wafer substrate in which image sensors, such as CCD and CMOS, were formed) In the same manner as in Examples 1 to 5 above, the blue color filter is formed on the imaging element forming surface side, the green color filter is formed by a known method using a green color resist, and the known method using a red color resist. By producing the red color filters, three color filters can be produced on the solid-state imaging device substrate. A solid-state imaging device including these three color filters is excellent in color purity and fastness in a blue color filter, is suppressed in color transfer, and is excellent in color reproducibility and sensitivity.

[Example 6]
(1) Preparation of colored photosensitive composition [positive type]-3.0 parts of the following resin P-1-1.8 parts of the following naphthoquinonediazide compound N-1-1.8 parts-Crosslinking agent: hexamethoxymethylolated melamine ... 0. 6 parts-Photoacid generator: TAZ-107 (manufactured by Midori Chemical Co., Ltd.) ... 1.2 parts-Fluorosurfactant (F-475, manufactured by DIC Corporation) ... 0.0005 parts-Solid dispersion: Exemplified 1 wt% ethyl lactate (EL) dispersion of compound 1-2 30 parts or more were mixed and dissolved to obtain a colored photosensitive composition [positive type].
In addition, in the 1 wt% ethyl lactate (EL) dispersion of Example Exemplary Compound 1-2, the average primary particle diameter of the solid fine particles was 82 nm. The solubility of Exemplified Compound 1-2 in ethyl lactate at 25 ° C. was 0.16% by mass.

  The resin P-1 and the naphthoquinone diazide compound (N-1) were synthesized as follows.

(2) Synthesis of Resin P-1 70.0 g of benzyl methacrylate, 13.0 g of methacrylic acid, 17.0 g of methacrylic acid-2-hydroxyethyl and 600 g of 2-methoxypropanol were charged into a three-necked flask, and a stirrer, reflux condenser A thermometer was attached, and a polymerization amount of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added at 65 ° C. under a nitrogen stream, followed by stirring for 10 hours. The obtained resin solution was added dropwise to 20 L of ion exchange water with vigorous stirring to obtain a white powder. This white powder was vacuum-dried at 40 ° C. for 24 hours to obtain 145 g of resin P-1. When the molecular weight was measured by GPC, the weight average molecular weight Mw = 28,000 and the number average molecular weight Mn = 11,000.

(3) Synthesis of naphthoquinonediazide compound (N-1) Trispamine PA (Honshu Chemical Co., Ltd.) 42.45 g, o-naphthoquinonediazide-5-sulfonyl chloride 61.80 g, and acetone 300 ml were charged into a three-necked flask and triethylamine at room temperature. 24.44g was dripped over 1 hour. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and then the reaction solution was poured into a large amount of water while stirring. The precipitated naphthoquinone diazide sulfonic acid ester was collected by suction filtration and vacuum-dried at 40 ° C. for 24 hours to obtain a naphthoquinone diazide compound (N-1).

  As a result of evaluating the colored photosensitive composition [positive type] obtained above by the method according to Example 1, alkali resistance, solvent resistance, color transfer, color purity, storage stability, heat resistance, and light resistance are obtained. It was found to be excellent.

[Examples 7 to 8]
(Preparation of dark color composition for barrier rib formation)
The dark-color composition K1 first measures K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 3, mixes at a temperature of 24 ° C. (± 2 ° C.), and stirs at 150 rpm for 10 minutes. While stirring, the amounts of methyl ethyl ketone (2-butanone), binder 2, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bis) shown in Table 3 Ethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine and surfactant 1 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and 150 rpm at a temperature of 40 ° C. (± 2 ° C.). For 30 minutes. In addition, the quantity of Table 3 is a mass part, and has the following composition in detail.

<K pigment dispersion 1>
・ Carbon black (Nippex 35 manufactured by Degussa) ... 13.1%
・ Dispersant (Compound B1 described below) 0.65%
-Polymer (Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 37,000) ... 6.72%
・ Propylene glycol monomethyl ether acetate: 79.53%

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

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

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

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

Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the dark color composition layer K1, and then a KOH developer (containing a nonionic surfactant, trade names: CDK-1, Fuji Film). Electronics Materials Co., Ltd. 100-fold diluted) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water is sprayed at a pressure of 9.8 MPa with an ultrahigh pressure cleaning nozzle to remove the residue, and a dark color composition layer K1 of the substrate is formed at an exposure amount of 2500 mJ / cm ^{2 in} the atmosphere. The film was post-exposed from the surface side and heated in an oven at 240 ° C. for 50 minutes to obtain a stripe-shaped partition wall having an opening having a thickness of 2.0 μm, an optical density of 4.0, and a width of 100 μm.

(Ink-repellent plasma treatment)
The substrate on which the barrier ribs were formed was subjected to ink repellent plasma treatment under the following conditions using a cathode coupling parallel plate type plasma treatment apparatus.

Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

(Method for preparing purple (V) ink)
Of the components shown in Table 4 below, a colorant and a solvent are mixed, and after premixing, zirconia beads having a diameter of 0.65 mm are used with a motor mill M-50 (manufactured by Eiger Japan) at a filling rate of 80%. Then, a solid dispersion is prepared by dispersing at a peripheral speed of 9 m / s for 25 hours, and other components are added to the prepared solid dispersion, and the mixture is stirred for 1 hour and filtered under reduced pressure through a microfilter having an average pore size of 0.45 μm. A purple (V) ink liquid (ink V-1 and ink V-2) was prepared.

Details of the components used are shown below.
Colorant: Exemplified compound 2-3
DPCA-60 (manufactured by Nippon Kayaku Co., Ltd. (KAYARAD DPCA-60)): caprolactone-modified dipentaerythritol hexaacrylate KF-353 (manufactured by Shin-Etsu Chemical Co., Ltd.): polyether-modified silicone oil

In the solid dispersion, the average primary particle size of the solid fine particles was 90 nm (Example 7) and 87 nm (Example 8), respectively.
The solubility of Exemplified Compound 2-3 in cyclohexanone at 25 ° C. was 0.33% by mass.

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

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

(Contrast measurement method)
When using a cold cathode tube light source with a diffusion plate as a backlight unit, a monochromatic substrate is installed between two polarizing plates (Lukeo's POLAX-15N), and the polarizing plates are installed in parallel Nicols. The contrast was determined by dividing the Y value of the chromaticity of the light passing therethrough by the Y value of the chromaticity of the light passing through when installed in crossed Nicols. A color luminance meter (BM-5A manufactured by Topcon Co., Ltd.) was used for the measurement of chromaticity. The monochromatic substrate was produced by the following method.
Using V ink (ink V-1 and ink V-2) constituting a color filter, a solid film is formed on a glass substrate by an ink jet method or a spin coat method, and prebaked (preliminary) in the same manner as the color filter formation. Heating (temperature 100 ° C., 2 minutes) and post-baking (post-heating) (temperature 220 ° C., 30 minutes) were performed to form a film thickness of 2 μm.

The measurement angle of the color luminance meter was set to 1 °, and the measurement was performed with a visual field of 5 mm on the sample. The amount of light of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 400 cd / m ² with no sample installed.

  When the contrast of the monochromatic substrates (two types) obtained above was measured, a value of 50000 or more was obtained with any monochromatic substrate.

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

(Change in spectral characteristics before and after ITO sputtering)
Before and after ITO sputtering, a spectral transmittance curve in a wavelength range of 400 nm to 700 nm was obtained using an ultraviolet-visible absorption spectrometer (V-570 manufactured by JASCO Corporation). When the amount of change in spectral transmittance at the maximum peak before and after sputtering is small, it means excellent heat resistance. It was found that the produced substrate had almost no change in spectral shape before and after ITO sputtering and had high heat resistance.

[Comparative Examples 3 to 4]
(Preparation of pigment dispersion)
17.5 parts by mass of C.I. Pigment Violet 23 (manufactured by Dainichi Seika Co., Ltd.), 2.5 parts by mass of pigment dispersant (compound B1) and solvent ((1,3-butanediol diacetate) 80 parts by mass of 1,3-BGDA) and MMPGAC (ethylene glycol monomethyl ether acetate), premixing, and then motor mill M-50 (manufactured by Eiger Japan), zirconia beads with a diameter of 0.65 mm Was dispersed at a peripheral speed of 9 m / s for 25 hours to prepare a pigment dispersion for V.

(Preparation of comparative ink)
As a comparative example, a pigment ink prepared in the amount shown in Table 5 below was prepared using the above pigment dispersion. The materials used are as follows.
DPS100 (Nippon Kayaku Co., Ltd.): KAYARAD DPS100
・ TMPTA (Nippon Kayaku Co., Ltd.): KAYARAD TMPTA
Surfactant: the aforementioned surfactant 1
V-40 (manufactured by Wako Pure Chemical Industries): Azobis (cyclohexane-1-carbonitrile)

(Method for producing color filter for evaluation)
Using the ink prepared above, the ink jet printer DMP-2831 manufactured by Fuji Film Dimatix was used to discharge the ink in the region (the concave portion surrounded by the convex portion) divided by the partition on the substrate obtained above. And then heated in an oven at 100 ° C. for 2 minutes. Next, the monochromatic color filter was produced by leaving still for 30 minutes in 220 degreeC oven.

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

(Continuous discharge stability evaluation)
Using the ink prepared above, the ejection stability was evaluated. The evaluation method was performed using an inkjet printer DMP-2831, manufactured by Fujifilm Dimatix, a head cartridge with a droplet ejection amount of 10 pL, and a droplet ejection frequency of 10 kHz, and the state when continuously ejected for 30 minutes was observed. Evaluation criteria were classified as follows.
-Evaluation criteria-
◎: Continuous discharge is possible without problems. ○: Slight non-ejection, ejection disturbance, etc. are observed during ejection, but it returns during ejection and there is almost no problem. △: Non-ejection and ejection disturbance occur during ejection. State that does not return during discharge but returns to normal by maintenance
×: Non-ejection and ejection disturbance occurred during ejection, normal ejection cannot be performed, and ejection is not restored by maintenance Maintenance is performed by purging with DMP-2831 (forcing ink from the nozzle by pressurizing ink in the head) And blotting (with the head nozzle surface slightly in contact with the cleaning pad and sucking ink from the nozzle surface).

(Evaluation of ejection stability after pause)
Using the ink prepared above, the ejection stability was evaluated. The evaluation method is the same as the continuous discharge stability evaluation, using an inkjet printer DMP-2831, manufactured by Fujifilm Dimatix, and a head cartridge with a droplet ejection amount of 10 pL, and ejecting once for 5 minutes at a droplet ejection frequency of 10 kHz. The state when the discharge was started again under the same conditions was observed. Evaluation criteria were classified as follows.
-Evaluation criteria-
◎: Discharge is possible at the same time as the droplet ejection instruction ○: Immediately after the droplet ejection instruction, a slight non-ejection and ejection turbulence are observed, but it returns during ejection and there is almost no problem △: Non-ejection and ejection turbulence Occurs, but does not return during discharge, but returns to normal state due to maintenance ×: Non-discharge, discharge disturbance occurs, discharge cannot be performed normally, and discharge does not return to normal level even during maintenance Purging with DMP-2831 (pressurizing ink in the head and forcibly ejecting ink from the nozzle) and blotting (with the head nozzle surface slightly in contact with the cleaning pad and sucking ink from the nozzle surface) were performed.

(Heat resistance evaluation)
The color filters of each color prepared above were placed in an oven heated to 230 ° C. and left for 1 hour, and then the hue was measured. For the measurement of hue, UV-560 (manufactured by JASCO Corporation) was used, and ΔEab before and after the evaluation was evaluated as ○ when less than 5. ΔEab is 5 or more and less than 15, and ΔEab is 15 or more.

(Chemical resistance evaluation)
The color filter of each color produced above was immersed in the chemical | medical agent (N-methylpyrrolidone, 2-propanol, 5% sulfuric acid aqueous solution, 5% sodium hydroxide aqueous solution) to evaluate for 20 minutes, and the hue before and behind that was measured. For the measurement of hue, UV-560 (manufactured by JASCO Corporation) was used, and ΔEab was less than 5 as ◯. ΔEab is 5 or more and less than 15, and ΔEab is 15 or more. The evaluation method for ΔEab is the same as described above.

  Table 6 below shows the evaluation results of the inkjet ink and the color filter.

  As shown in Table 6, the ink jet inks of Examples 7 and 8 were excellent in storage stability and ejection stability. On the other hand, Comparative Example 6 using a conventional pigment ink has poor ejection stability and lacks practicality.

[Example 9]
(Adjustment of water-based colored ink V-3)
A methacrylic acid-methacrylic acid ester copolymer aqueous solution 25.5 represented by Dispersant Solution 10 described on page 22 of International Publication No. WO2006 / 064193 using 5 parts by mass of the exemplified compound (5) as a polymer dispersant. 19.5 parts of water and 100 parts of zirconia beads having a diameter of 0.1 mm were mixed for 6 hours at 300 revolutions per minute using a planetary ball mill. After the completion of dispersion, zirconia beads were separated to obtain a purple solid dispersion V-3.

[Example 10]
(Adjustment of water-based colored ink V-4)
A purple solid dispersion V-4 was obtained in the same manner except that the exemplary compound (5) of Example 9 was changed to the exemplary compound (1-1).

  The solid dispersions obtained in Examples 9 and 10 were No. When the bar No. 3 was used and a bar coater was used to apply bar to photo mat paper <Pigment only> manufactured by Seiko Epson Corporation, a clear purple solid image was obtained. In particular, Example 10 in which raked pyromethene was solid-dispersed gave an image with high color purity and transparency.

As shown above, it is very useful to use a dipyrromethene metal complex in a solid dispersion.
Conventional dipyrromethene-based metal complexes have excellent color purity, but there is room for improvement in various fastnesses (light resistance and heat resistance). For this reason, the improvement effect is acquired by using solid-dispersed like this invention. Among solid dispersions, rake formation is particularly useful in that it does not reduce color purity and transparency. Moreover, since this solid dispersion can be applied as a general-purpose colorant (such as a writing instrument) in addition to a conventionally known colored photosensitive composition, it has a high industrial utility value.

Claims (13)

Containing a solvent and a colorant insoluble in the solvent,
The colorant is a complex in which a compound represented by the following general formula (1) or a tautomer thereof is coordinated to a metal or a metal compound and is insoluble in the solvent, or the following general A solid dispersion, wherein the complex represented by the formula (1) or a tautomer thereof is coordinated to a metal or a metal compound and is insolubilized in the solvent.


[In General Formula (1), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. ] The complex in which the compound represented by the general formula (1) or a tautomer thereof is coordinated to a metal or a metal compound is insolubilized in the solvent is a metal complex represented by the following general formula (2) The solid dispersion according to claim 1 which is a compound or a tautomer thereof.


[In general formula (2), A removed one hydrogen atom from any position of the complex represented by the compound represented by general formula (1) or a tautomer thereof coordinated to a metal or a metal compound. It is a residue, n represents 2 or 3, and M represents an n-valent metal ion. ] The compound represented by the general formula (1) or a tautomer thereof coordinated to a metal or a metal compound is a compound represented by the following general formula (3) or a tautomer thereof. The solid dispersion according to claim 1 or 2.


[In General Formula (3), R ^{2 to} R ⁵ each independently represents a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal or a metal compound, and X ³ represents 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), nitrogen. An atom, an oxygen atom, or a sulfur atom, and X ⁴ represents NRa (Ra 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); Represents an oxygen atom or a sulfur atom, and 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), a nitrogen atom. , or represents a carbon atom, Y ² is a nitrogen atom, or represents a carbon atom, R ⁸ and R ⁹ are each independently an alkyl group, an alkenyl group, aryl It represents 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-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. ]   The coloring photosensitive composition containing the solid dispersion liquid of any one of Claims 1-3.   An inkjet ink containing the solid dispersion according to any one of claims 1 to 3.   A color filter comprising the colored photosensitive composition according to claim 4 or the inkjet ink according to claim 5.   A step of applying the colored photosensitive composition according to claim 4 on a support to form a colored layer, a step of exposing the formed colored layer through a mask, and developing the exposed colored layer And a step of forming a colored pattern.   Furthermore, the manufacturing method of the color filter of Claim 7 which has the process of irradiating an ultraviolet-ray to the formed colored pattern after the process of developing and forming a colored pattern.   A step of preparing a substrate having a concave portion partitioned by a partition; and a step of forming a colored pixel of a color filter by applying a droplet of the ink jet ink according to claim 5 to the concave portion by an ink jet method. The manufacturing method of the color filter which has these.   A solid-state imaging device comprising the color filter according to claim 6.   A display device comprising the color filter according to claim 6. A metal complex compound represented by the following general formula (2) and a tautomer thereof.

[In general formula (2), A removed one hydrogen atom from an arbitrary position of a complex represented by the following general formula (1) or a tautomer thereof coordinated to a metal or a metal compound. It is a residue, n represents 2 or 3, and M represents an n-valent metal ion. ]


[In General Formula (1), R < ¹ > -R < ⁶ > represents a hydrogen atom or a substituent each independently. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. ] The compound represented by the general formula (1) or a tautomer thereof coordinated to a metal or a metal compound is a compound represented by the following general formula (3) or a tautomer thereof. The metal complex compound according to 12, and a tautomer thereof.


[In General Formula (3), R ^{2 to} R ⁵ each independently represents a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal or a metal compound, and X ³ represents 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), nitrogen. An atom, an oxygen atom, or a sulfur atom, and X ⁴ represents NRa (Ra 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); Represents an oxygen atom or a sulfur atom, and 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), a nitrogen atom. , or represents a carbon atom, Y ² is a nitrogen atom, or represents a carbon atom, R ⁸ and R ⁹ are each independently an alkyl group, an alkenyl group, aryl It represents 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-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring. A ring may be formed. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. ]