JP5398586B2 - Colored curable composition, color filter, method for producing the same, and solid-state imaging device - Google Patents

Description

  The present invention relates to a colored curable composition, a color filter, a method for producing the same, and a solid-state imaging device.

  As a method for producing a color filter used for a liquid crystal display element (LCD or the like) or a solid-state image pickup element (CCD or CMOS), a pigment dispersion method is widely known.

The pigment dispersion method is a method for producing a color filter by a photolithography method using a colored photosensitive composition in which a pigment is dispersed in various photosensitive compositions. This is a method suitable for producing a color filter with high positional accuracy, a large screen, and high definition because patterning is performed by a photolithography method. When a color filter is produced by a pigment dispersion method, a photosensitive composition is applied on a glass substrate by a spin coater or a roll coater to form a coating film, and a colored pixel is formed by pattern exposure and development of the coating film. The color filter is obtained by repeating this operation for each color.
As a colored photosensitive composition using a pigment, for example, a blue colored composition for a color filter containing a phthalocyanine pigment described in Patent Document 1 is known.

  In the case of manufacturing a display element such as a liquid crystal display element or a solid-state imaging element by providing a color filter using a pigment, a pigment having a finer particle size is required from the viewpoint of improving the contrast. This is due to a factor that the polarization axis rotates due to light scattering, birefringence, and the like by the pigment. If the pigment is not sufficiently refined, light is scattered and absorbed by the pigment, the light transmittance is lowered, the contrast is lowered, and further, the curing sensitivity at the time of pattern exposure is lowered.

  In particular, in color filters for solid-state image sensors, in recent years, further higher definition has been desired. Therefore, it is difficult to further improve the resolution with a conventional pigment dispersion system. That is, there is a problem that color unevenness occurs due to the influence of coarse pigment particles. Therefore, the pigment dispersion system is not suitable for applications requiring a fine pattern with a pixel size of 0.7 to 3.0 μm square, such as a solid-state imaging device.

In response to such a situation, techniques for using dyes instead of pigments have been proposed. However, dyes are generally known to be inferior in light resistance and heat resistance as compared to pigments, which may cause problems in the performance of color filters. In addition, the dye has low solubility in the photosensitive composition, and has a problem that the dye is precipitated due to low stability over time in a liquid preparation or a coating film.
With respect to these problems, a colored curable composition that can form a color filter having excellent storage stability and high light resistance by using a dye containing a dipyrromethene compound and a phthalocyanine dye in combination has been proposed ( For example, see Patent Document 2.)
Moreover, the coloring curable composition which combined dye and a pigment is also known (for example, refer patent document 3).

JP 2001-33616 A JP 2008-292970 A US Patent Application Publication No. 2008/0171271

However, when a colored pattern is formed using a colored curable composition containing a dye containing a dipyrromethene compound and a phthalocyanine pigment, the color of the colored pattern is laminated particularly when the colored pattern is subjected to heat treatment. It has become clear that there is a case where a phenomenon (hereinafter also referred to as “color bleeding”) occurs in a layer or an adjacent layer.
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 colored curable composition capable of forming a colored pattern with suppressed color bleeding.
It is another object of the present invention to provide a color filter in which color blur is suppressed, a method for manufacturing the color filter, and a solid-state imaging device including the color filter.

Specific means for solving the above problems are as follows.
<1> A colored curable composition containing a phthalocyanine pigment, a dye multimer containing a polymerizable group and a group derived from a dipyrromethene dye, a polymerization initiator, a polymerizable compound, and a solvent.
<2> The colored curable composition according to <1>, wherein the dye multimer includes, as a repeating unit, a structural unit having a polymerizable group and a structural unit having a group derived from a dipyrromethene dye.
<3> The colored curable composition according to <1> or <2>, wherein the polymerizable group is an ethylenically unsaturated group.
<4> The colored curable composition according to any one of <1> to <3>, wherein the dipyrromethene dye is a dipyrromethene dye represented by the following general formula (C).

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

<5> The colored curable composition according to any one of <1> to <4>, further containing a dioxazine pigment.
<6> The dioxazine pigment is C.I. I. The colored curable composition according to <5>, which is CI Pigment Violet 23.

<7> The colored curable composition according to any one of <1> to <6>, wherein the polymerization initiator is an oxime polymerization initiator.
<8> A color filter using the colored curable composition according to any one of <1> to <7>.
<9> On the support, a step (A) of applying the colored curable composition according to any one of <1> to <7> to form a colored curable composition layer;
A step (B) in which the colored curable composition layer formed in the step (A) is exposed through a mask and then developed to form a colored pattern;
The manufacturing method of the color filter which has this.
<10> A solid-state imaging device including the color filter according to <8>.

ADVANTAGE OF THE INVENTION According to this invention, the colored curable composition which can form the coloring pattern in which color bleeding was suppressed can be provided.
In addition, according to the present invention, it is possible to provide a color filter in which color bleeding is suppressed, a method for manufacturing the color filter, and a solid-state imaging device including the color filter.

≪Colored curable composition≫
First, the colored curable composition of the present invention will be described.
The colored curable composition of the present invention includes a phthalocyanine pigment, a dye multimer containing a polymerizable group and a group derived from a dipyrromethene dye, a polymerization initiator, a polymerizable compound, and a solvent.
When a colored pattern is formed using a colored curable composition containing a dye containing a dipyrromethene compound and a phthalocyanine pigment, when the colored pattern is subjected to a heat treatment, a layer or a laminate in which the color of the colored pattern is adjacent There is a case where a phenomenon (color bleeding) of bleeding into the applied layer occurs. This is presumably because the dye containing the dipyrromethene compound easily moves to an adjacent layer or a laminated layer by heat treatment.
Therefore, by setting the colored curable composition to the configuration of the present invention, color bleeding when a colored pattern is formed is suppressed.
The cause of suppression of color bleeding is not clear, but as a colorant containing a dipyrromethene compound, by using a dye multimer containing a polymerizable group and a group derived from a dipyrromethene dye, adjacent layers or layers are laminated. This is presumably because the movement of the colorant to the layer is suppressed. However, the present invention is not limited by this assumption.
Hereinafter, each component of the colored curable composition of the present invention will be described.

<Phthalocyanine pigment>
The phthalocyanine pigment used in the present invention 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.

  The content of the phthalocyanine pigment in the colored curable composition in the present invention is preferably 10% by mass to 60% by mass, and 20% by mass to 60% by mass with respect to the total solid content component of the colored curable composition. More preferably, 35% by mass to 50% by mass is most preferable.

<Dye multimer containing polymerizable group and group derived from dipyrromethene dye>
The colored curable composition of the present invention contains at least one dye multimer (hereinafter sometimes simply referred to as “polymerizable group-containing dye multimer”) containing a polymerizable group and a group derived from a dipyrromethene dye. contains. The polymerizable group-containing dye multimer functions as, for example, a colorant in the colored curable composition of the present invention.

Since the polymerizable group-containing dye multimer is a dye multimer containing a group derived from a dipyrromethene dye, it has a good hue and a high extinction coefficient, and the colored curable composition of the present invention is thinned. Even in such a case, a cured film having excellent color purity can be formed.
The group derived from the dipyrromethene dye contained in the polymerizable group-containing dye multimer may be one kind or two or more kinds.

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

The polymerizable group-containing dye multimer has a structural unit having a polymerizable group and a structural unit having a group derived from a dipyrromethene dye (hereinafter, simply referred to as “structural unit having a group derived from a dye”). Are preferably included as repeating units.
The polymerizable group-containing dye multimer may contain other constituent units other than “structural unit having a polymerizable group” and “structural unit having a group derived from a dye”.
In the polymerizable group-containing dye multimer, from the viewpoint of thinning the color filter, it is preferable to include 60 mass% to 99 mass% of a structural unit having a group derived from the dye in a mass ratio of 70 mass%. It is more preferable to contain -97 mass%, and it is further more preferable to contain 80 mass%-95 mass%.
Further, from the viewpoint of heat resistance and solvent resistance, the structural unit having a polymerizable group is preferably contained in an amount of 1% by mass to 40% by mass, more preferably 3% by mass to 30% by mass. More preferably, the content is 20% by mass to 20% by mass.
The weight average molecular weight (polystyrene conversion value measured by GPC method) of the polymerizable group-containing dye multimer is not particularly limited, but is preferably 3000 to 50000 from the viewpoint of more effectively suppressing color bleeding. -30000 is more preferable, and 7000-20000 is particularly preferable.

  The structural unit having a group derived from the dye may be, for example, radically polymerizing a dye compound in which a polymerizable group (for example, acryloxy group, methacryloxy group, styryl group, etc.) is introduced into the dipyrromethene dye skeleton, It can introduce | transduce into a polymeric group containing pigment | dye multimer. Also, a dye compound in which a group capable of polycondensation or polyaddition reaction is introduced into the dipyrromethene dye skeleton can be introduced into the polymerizable group-containing dye multimer by reacting with a polyfunctional crosslinking agent.

The structural unit having a polymerizable group can be introduced into the polymerizable group-containing dye multimer by the following method, for example.
That is, a structure in which a multimer is obtained by copolymerization of the dye compound and a copolymer component having no dye skeleton (for example, methacrylic acid, acrylic acid, hydroxyethyl methacrylate, etc.), and then derived from the copolymer component By adding a polymerizable compound having a group that reacts with the unit (for example, glycidyl methacrylate, methacryloxyethyl isocyanate, etc.), a structural unit having a polymerizable group can be introduced.
In the dye compound, a polymerizable group-containing dye is introduced by introducing into the dipyrromethene dye skeleton a polymerizable group that is different from a polymerizable group that causes multimerization of the dye compound, and polymerizing the dye compound. Multimers can also be obtained.

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

(1) Dipyrromethene dye The dipyrromethene dye is not particularly limited, but a dipyrromethene dye represented by the following general formula (C) is preferably used in terms of light resistance and heat resistance.

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

Each substituent of the general formula (C) will be described in detail.
R ^{2 to} R ⁵ each independently represent a hydrogen atom or a substituent, and examples of the substituent include a halogen atom (eg, fluorine, chlorine, bromine), an alkyl group (preferably having 1 to 48 carbon atoms, More preferably, it is a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl. , Dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, 1-adamantyl), an 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 having 6 to 48 carbon atoms, more preferably 6 carbon atoms). 24 aryl groups such as phenyl and naphthyl, and heterocyclic groups (preferably 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 having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms). Silyl group, for example, trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl, t-hexyldimethylsilyl), hydroxy group, cyano group, nitro group, alkoxy group (preferably having 1 to 48 carbon atoms, more preferably Is an alkoxy group having 1 to 24 carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy Xoxy, isopropoxy, t-butoxy, dodecyloxy, cycloalkyloxy groups, for example, cyclopentyloxy, cyclohexyloxy), aryloxy groups (preferably having 6 to 48 carbon atoms, more preferably aryloxy having 6 to 24 carbon atoms) Group, for example, phenoxy, 1-naphthoxy), a heterocyclic oxy group (preferably a C1-C32, more preferably a C1-C18 heterocyclic oxy group, for example, 1-phenyltetrazol-5-oxy 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 having 2 to 48 carbon atoms, More preferably, it is an acyloxy group having 2 to 24 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy), an alkoxycarbonyloxy group (preferably having 2 to 48 carbon atoms, more preferably an alkoxy having 2 to 24 carbon atoms). A carbonyloxy group, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy, cycloalkyloxycarbonyloxy (for example, cyclohexyloxycarbonyloxy)), an aryloxycarbonyloxy group (preferably having 7 to 32 carbon atoms, more preferably carbon An aryloxycarbonyloxy group having 7 to 24, for example, phenoxycarbonyloxy), a carbamoyloxy group (preferably having 1 to 48 carbon atoms, more preferably a carbamoyloxy group having 1 to 24 carbon atoms, For example, N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy, N-ethyl-N-phenylcarbamoyloxy), a sulfamoyloxy group (preferably having 0 to 32 carbon atoms, more preferably A sulfamoyloxy group having 1 to 24 carbon atoms, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), an alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably An alkylsulfonyloxy group having 1 to 24 carbon atoms, such as 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 carbon atoms, such as anilino or N-methylanilino), a heterocyclic amino group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic amino group having 1 to 18 carbon atoms, For example, 4-pyridylamino), carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetamido, benzamido, tetradecanamido, pivaloylamide, cyclohexaneamido), ureido group (Preferably a ureido group having 1 to 32 carbon atoms, more preferably 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 it is an imide group having 24 or less carbon atoms, such as N-succinimide and N-phthalate. Imide), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonyl Amino, cyclohexyloxycarbonylamino), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as phenoxycarbonylamino), sulfonamide group (preferably Is a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide, cyclohexane. Sulfonamides), sulfamoylamino groups (preferably sulfamoylamino groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as N, N-dipropylsulfamoylamino, N-ethyl). -N-dodecylsulfamoylamino), 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) Ilylamino group includes, for example, diethoxyphosphinoylamino, dioctyloxyphosphinoylamino).

In the case where the substituents of R ² and R ⁵ are further substitutable substituents, for example, they may be substituted with the substituents described above or may be substituted with two or more substituents. These substituents may be the same or different.

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

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

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

For example, the alkyl group, aryl group, and heterocyclic group of R ⁷ may be substituted with the substituents described in R ^{2 to} R ⁵ , and may be substituted with two or more substituents. These substituents may be the same or different.

In the general formula (C), Ma represents a metal atom or a metal compound. The metal atom or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or Divalent metal chlorides are included. For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe , etc., and _{AlCl, InCl, FeCl, TiCl 2} , SnCl 2, SiCl 2, GeCl 2 , etc. Metal chlorides, metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are included.

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

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

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

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

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

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

In the general formula (C), R ⁸ and Y ¹ are bonded to each other and a carbon atom together with 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 7-membered ring (eg, cyclo Heptane, hexamethyleneimine).

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

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

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

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

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

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

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

  For the method of synthesizing the dipyrromethene dye, the method of polymerizing the dye, and the method of introducing the polymerizable group into the dye, use the methods described in JP2007-147784A, JP2008-292970A, and the like. Can do.

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

(3) Structural Unit Having Polymerizable Group Examples of the structural unit having a polymerizable group contained in the polymerizable group-containing dye multimer include the following structural units.
That is, a polymerizable compound having a group that reacts with the structural unit (for example, methacrylic acid, acrylic acid, hydroxyethyl methacrylate, etc.) derived from a copolymerized component copolymerized with the above-described dye compound (for example, , Glycidyl methacrylate, methacryloxyethyl isocyanate, and the like).

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

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

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

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

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

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

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

Table 1 below shows specific compound examples of the polymerizable group-containing dye multimer of the present invention, but the present invention is not limited thereto.
In Table 1 below, the number of each unit corresponds to the number of the exemplified compound described above.

  In Table 1, the “alkali-soluble unit” column shows a copolymerized monomer.

The content of the polymerizable group-containing dye multimer in the colored curable composition of the present invention varies depending on the molecular weight and the molar extinction coefficient, but is 5% by mass to 40% by mass with respect to the total solid components of the composition. Is preferable, 10 mass%-30 mass% is more preferable, 15 mass%-25 mass% is especially preferable.
The mass ratio of the phthalocyanine pigment and the polymerizable group-containing dye multimer [polymerizable group-containing dye multimer / phthalocyanine pigment] in the colored curable composition of the present invention is 0.1 to 3.0. Preferably, 0.1 to 2.0 is more preferable, and 0.5 to 1.0 is particularly preferable.
When the mass ratio [polymerizable group-containing dye multimer / phthalocyanine pigment] is 0.1 or more, the hue characteristics can be adjusted more effectively.
When the mass ratio [polymerizable group-containing dye multimer / phthalocyanine pigment] is 3.0 or less, the light resistance can be improved more effectively.

<Dioxazine pigment>
The colored curable composition of the present invention preferably further contains a dioxazine pigment.
When the colored curable composition of the present invention contains a dioxazine pigment, the light resistance of the formed colored pattern is further improved.
Examples of the dioxazine pigment include C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 32, C.I. I. Pigment violet 37, among which C.I. I. Pigment Violet 23 is preferable.

  When the colored curable composition of the present invention contains a dioxazine-based pigment, the content thereof is preferably 0.1% by mass to 30% by mass in the total solid content of the colored curable composition, and 0.5% by mass. -20% by mass is more preferable, and 1% by mass to 10% by mass is particularly preferable.

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

<Polymerizable compound>
The colored curable composition of the present invention contains a polymerizable compound.
Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond. Specifically, it is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and their (co) polymers. 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 paragraphs 0095 to 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.

  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 numbers 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

  The content of the polymerizable compound described above in the colored curable composition is preferably from 5 to 90 mass%, more preferably from 10 to 80 mass%, more preferably from 15 to 50 mass%, based on the solid content of the composition. Is particularly preferred. When the content is within the above range, it is possible to maintain a sufficient degree of cure and elution of the unexposed area, maintain a sufficient degree of cure of the exposed area, and significantly reduce the elution of the unexposed area. Can be prevented.

<Polymerization initiator>
The colored curable composition of the present invention contains a polymerization initiator.
The polymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound described above, and is preferably selected from the viewpoints of properties, initiation efficiency, absorption wavelength, availability, cost, and the like.

As the polymerization initiator, a photopolymerization initiator is preferable, and as the photopolymerization initiator, for example, at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, 3-aryl substitution Coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs [0070] to [0077] of JP-A No. 2004-295116.
Among these, 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-based photopolymerization initiator is not particularly limited. For example, JP 2000-80068 (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 curable composition of the present invention. Also good.

A photoinitiator can be contained individually by 1 type or in combination of 2 or more types.
The content of the photopolymerization initiator in the total solid content of the colored curable composition (total content in the case of two or more) is 3% by mass to 20% by mass from the viewpoint of more effectively obtaining the effects of the present invention. % Is preferable, 4% by mass to 19% by mass is more preferable, and 5% by mass to 18% by mass is particularly preferable.

<Solvent>
The colored curable composition of the present invention contains a solvent.
The solvent is basically not particularly limited as long as it can satisfy the solubility of each coexisting component and the coating property when a colored curable composition is used, and in particular, the solubility, coating property, and safety of the binder. It is preferable to select in consideration of the properties.

  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, 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-ethoxy Methyl propionate, 3-ethoxypropyl And 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 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.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-mentioned components, and the solubility and the improvement of the coating surface state when an alkali-soluble binder is included. In this case, particularly preferably, 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 solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.

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

<Dispersant>
The colored curable composition of the present invention preferably contains a dispersant.
As the dispersant, a known pigment dispersant or surfactant is used.
As the dispersant, many kinds of compounds are used. For example, phthalocyanine derivatives (commercially available product EFKA-745 (manufactured by Efka)), Solsperse 5000 (manufactured by Nippon Lubrizol Co., Ltd.); organosiloxane polymer KP341 (Shin-Etsu) Chemical Industries, Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (above, manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, poly Nonionic surfactants such as oxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (above, manufactured by Yusho Co., Ltd.), etc. Anionic surfactants; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), D Polymer dispersing agents such as Perth Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (Sannopco Co., Ltd.); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000 , 26000, 28000, etc. (manufactured by Nippon Lubrizol Corporation); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (above, manufactured by Asahi Denka Co., Ltd.), and Isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.) can be mentioned.

  The content of the dispersant in the colored curable composition of the present invention is preferably 1% by mass to 80% by mass, more preferably 5% by mass to 70% by mass, and more preferably 10% by mass to 60% by mass with respect to the pigment. Is most preferred.

<Other ingredients>
The colored curable composition of the present invention may further contain other components such as a resin and a cross-linking agent in addition to the above-described components as long as the effects of the present invention are not impaired.

-Resin-
As the resin, an alkali-soluble binder can be suitably used.
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be 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.

  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 curable composition of this invention contains the said polymer (a), the heat resistance and transparency of the cured coating film formed using this composition improve more.
In the 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 v, 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 binder, developability, from the viewpoint of liquid viscosity, weight average molecular weight (measured in terms of polystyrene by GPC method) is preferably a polymer of 1,000 to 2 × 10 ^5, the weight of the 2000-1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.
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.

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

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

-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, F780, F781 (above, DIC Corporation), Florard FC430, FC431, FC171 (above, 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.), CW-1 (manufactured by GENECA), etc. It is done.

Specific examples of cationic surfactants include phthalocyanine derivatives (commercially available product EFKA-745 (manufactured by Morishita Sangyo)), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) Polymer Polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
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. “SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-444 (4) (5) (6) (7) 6”, “TSF-” manufactured by Toshiba Silicone Co., Ltd. 44 60 ”,“ TSF-4452 ”,“ KP341 ”manufactured by Silicone Co., Ltd.,“ BYK323 ”,“ BYK330 ”manufactured by Big Chemie.
Two or more surfactants may be combined.

-Organic carboxylic acid-
In the case where the alkali solubility in the non-exposed area is promoted and the developability of the colored curable composition is further improved, the composition has 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-
If necessary, the colored curable composition may contain various additives such as fillers, polymer compounds other than those described above, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like. it can. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
The colored curable composition of the present invention 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 curable composition>
The colored curable composition of the present invention is prepared by mixing the above-mentioned essential components and, if necessary, optional components.
In preparing the colored curable composition, the components constituting the colored curable composition may be combined at once, or may be sequentially added after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
The colored curable composition prepared as described above is preferably filtered using a Millipore filter having a pore size of about 0.01 μm to 3.0 μm, more preferably about 0.05 μm to 0.5 μm. Can be used for use.

Since the colored curable composition of the present invention can suppress color bleeding when a colored pattern is formed, it is a colored pixel such as a color filter used in a liquid crystal display device (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.). It can be suitably used for forming.
In particular, considering that the smaller the colored pixel, the stronger the effect of color bleeding, the pixel size (colored pattern size) is 0.7 μm to 3.0 μm square, for forming colored pixels for color filters for solid-state image sensors. The pixel size (colored pattern size) is more suitable for forming a colored pixel of a color filter for a solid-state imaging device having a pixel size (colored pattern size) of 0.7 μm to 2.0 μm square. Is particularly suitable for forming colored pixels of a color filter for a solid-state imaging device having a size of 0.7 μm to 1.5 μm square.

≪Color filter and manufacturing method≫
Next, a method for producing a color filter using the colored curable composition of the present invention (a method for producing a color filter of the present invention) will be described.
The color filter manufacturing method of the present invention is formed by the steps (A) and (A) of forming a colored curable composition layer by applying the colored curable composition of the present invention on a support. The colored curable composition layer is exposed through a mask and then developed to form a colored pattern (B).
In the method for producing a color filter of the present invention, in particular, the step (C) of irradiating the colored pattern formed in the step (B) with ultraviolet rays and the colored pattern irradiated with the ultraviolet rays in the step (C). It is preferable to further include a step (D) of performing heat treatment.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.

-Process (A)-
In the method for producing a color filter of the present invention, first, the colored curable composition of the present invention described above is applied onto a support by a coating method such as spin coating, cast coating, roll coating, and the like. A composition layer is formed, and then pre-curing (pre-baking) is performed as necessary, and the colored curable composition layer is dried.

  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 spin-coating the colored curable composition on the support, in order to reduce the amount of dripping of the liquid, before dropping the colored curable composition, by dropping and rotating an appropriate organic solvent, The familiarity of the colored curable 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 curable composition layer formed from the colored curable composition is appropriately selected depending on the purpose, but is generally preferably 0.2 μm to 5.0 μm. More preferably, it is 3 μm to 2.5 μm, and most preferably 0.3 μm to 1.5 μm. In addition, the thickness of the coloring curable composition layer here is a film thickness after prebaking.

-Process (B)-
Subsequently, in the method for producing a color filter of the present invention, the colored curable composition layer formed on the support is exposed through a mask.
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. It is preferable in that it matches the photosensitive wavelength of the resist (colored curable 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 curable composition) is 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 curable composition layer can be heated at 70 ° C. to 180 ° C. for about 0.5 minutes to 15 minutes using a hot plate or oven before the next development processing.
The exposure can be performed while flowing nitrogen gas in the chamber in order to suppress oxidation fading of the coloring material in the colored curable composition layer.

Subsequently, the colored curable composition layer after the exposure is developed with a developer. Thereby, a colored pattern (resist pattern) can be formed.
As long as the developer dissolves the uncured portion (unexposed portion) of the colored curable composition layer and does not dissolve the cured portion (exposed portion), a combination of various organic solvents or an alkaline aqueous solution may be used. it can. 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, in the method for producing a color filter of the present invention, if necessary, post-heating and / or post-exposure can be performed on the colored pattern formed by development to promote curing of the colored pattern.

-Step (C)-
In particular, in the method for producing a color filter of the present invention, adjacent pixels or layers are laminated by performing post-exposure by ultraviolet irradiation on a colored pattern (pixel) formed from the colored curable composition of the present invention. It is possible to more effectively suppress color bleeding on the upper and lower layers. This color blur is a unique problem that occurs when a dye is used as a color material, and can be reduced by post-exposure by ultraviolet irradiation as described below.

(Post-exposure by UV irradiation)
In the post-exposure by ultraviolet irradiation, the amount of irradiation light [mJ / cm ² ] 10 times or more of the exposure amount [mJ / cm ² ] in the exposure process before development is applied to the colored pattern after the development processing as described above. It is preferable to irradiate ultraviolet light (UV light).
In addition, by irradiating the developed colored pattern with ultraviolet light (UV light) for a predetermined time between the development process and the heat treatment in the step (D) described later, the color bleeds when heated later. Can be more effectively prevented, and the light resistance is further improved.

As a light source for irradiating ultraviolet 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% with respect to the integrated irradiation illuminance of all the wavelength light in the ultraviolet light. What can irradiate the light which is the above 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 bleeding between adjacent pixels and the upper and lower layers and the effect of improving light resistance can be further enhanced. From this point, post-exposure by ultraviolet irradiation is performed using a light source different from a light source such as an i-line or the like used for exposure in the above-described step (B), specifically, a high-pressure mercury lamp, a low-pressure mercury lamp, or the like. Is preferred. Among these, for the same reason as described above, the irradiation illuminance [mW / cm ² ] of light having a wavelength of 275 nm or less is preferably 7% or more with respect to the integrated irradiation illuminance of all wavelengths of 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.

From the viewpoint of further suppressing color bleeding and light resistance, the ultraviolet 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 aforementioned step (B). Especially, the irradiation light quantity of ultraviolet light is preferably 12 times or more and 200 times or less, and more preferably 15 times or more and 100 times or less the exposure amount at the time of exposure in the above-described step (B).

In this case, the integrated irradiation illuminance in the irradiated ultraviolet light is preferably 200 mW / cm ² or more. When the integrated illumination illuminance is 200 mW / cm ² or more, it is possible to more effectively enhance the effect of suppressing color bleeding between adjacent pixels and the upper and lower layers and the effect of improving light resistance. Among ^them, preferred is ^{250mW / cm 2 ~2000mW / cm 2} , 300mW / cm 2 ~1000mW / cm 2 is more preferable.

-Process (D)-
Heat treatment is preferably performed on the colored pattern that has been post-exposed by ultraviolet irradiation as described above. The colored pattern can be further cured by heating (so-called post-baking) the formed colored pattern.
This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. In addition, the heating time is preferably 30 seconds to 30000 seconds, and more preferably 60 seconds to 1000 seconds.

In the method for producing a color filter of the present invention, instead of post-exposure by ultraviolet irradiation as in the above-mentioned step (C), post-exposure by g-line, h-line, i-line, KrF, ArF, electron beam, X-ray, etc. Exposure may be performed.
In the case of post-exposure by these means, the irradiation time is 10 seconds to 180 seconds, preferably 20 seconds to 120 seconds, and more preferably 30 seconds to 60 seconds.

In the method for producing a color filter of the present invention, the post-exposure by the ultraviolet irradiation as in the above-described step (C) may not be performed, and only the post-exposure as in the above-described step (D) may be performed.
Further, either post-exposure or post-heating may be performed first, but it is preferable to perform post-exposure prior to post-heating. This is because by promoting curing by post-exposure, deformation of the shape due to thermal sagging (spheroidization of the rectangular pattern) and soaking (reflowing of the pattern lower layer) of the colored pattern seen in the post-heating process is suppressed.

The colored pattern thus obtained constitutes a pixel in the color filter.
In the production of a color filter having pixels of a plurality of hues, the above-described steps (A) and (B), and further, if necessary, the steps (C) and (D) are adjusted to the desired number of colors. Repeat it.
In addition, whenever formation, exposure, and development of a monochromatic colored curable composition layer are completed (for each color), the above-described step (C) and / or step (D) may be performed, or a desired one may be performed. After the formation, exposure, and development of all the colored curable composition layers having the number of colors are completed, the above-described step (C) and / or step (D) may be performed collectively.

Even when the colored curable composition according to the present invention adheres to, for example, the nozzle of the coating apparatus discharge section, the piping section of the coating apparatus, the inside of the coating apparatus, etc., it can be easily cleaned and removed using a known cleaning liquid. . In this case, in order to perform more efficient cleaning and removal, it is preferable to use a solvent contained in the colored curable composition according to the present invention as a 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-A 2007-2101, JP-A 2007-2102, JP-A 2007-281523 and the like are also preferably used as cleaning liquids for cleaning and removing the colored curable 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 curable composition, a surfactant related to the present composition described above may be added to the cleaning liquid.

Since the color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) uses the colored curable composition of the present invention, color bleeding is suppressed.
Therefore, the color filter of the present invention can be used for a liquid crystal display element, a solid-state imaging element such as a CCD image sensor or a CMOS image sensor, and a camera system using the same. In addition, it is suitable for use in a solid-state imaging device that requires a good rectangular cross-sectional profile, particularly for a high-resolution CCD device, CMOS, or the like exceeding 1 million pixels. The preferable pixel size of the solid-state imaging device is as described in the section of “colored curable composition”.

≪Solid-state imaging device≫
The solid-state imaging device of the present invention includes the color filter of the present invention. The color filter of the present invention has suppressed color blurring, and a solid-state imaging device provided with this color filter can obtain excellent color reproducibility.

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, a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a CCD image sensor (solid-state imaging device) is provided on a support, and the color filter of the present invention is provided on the transfer electrode. The microlenses are stacked.

  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.

≪Liquid crystal display device≫
The color filter of the present invention is suitable as a color filter for a liquid crystal display device because color bleeding is suppressed and hue is excellent.
A liquid crystal display device including such a color filter can display a high-quality image.
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 Book 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)".

The liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film in addition to the color filter of the present invention. 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. Have been described.

  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.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, both “part” and “%” are based on mass.

<Synthesis of Exemplified Compound 101 (Dye Multimer)>
Dye unit 1-1 (3.45 g), polymerizable unit G-1 (1.55 g), methacrylic acid (0.5 g), n-dodecanethiol 420 mg are dissolved in 28.3 ml of propylene glycol monomethyl ether acetate (PGMEA). The mixture was stirred at 85 ° C. under nitrogen and 478 mg of dimethyl 2,2′-azobis (2-methylpropionate) was added. Thereafter, 478 mg of dimethyl 2,2′-azobis (2-methylpropionate) was additionally added every 2 hours, the temperature was raised to 90 ° C., and the mixture was further stirred for 2 hours. After completion of the reaction, the reaction solution was added dropwise into 400 ml of acetonitrile, and the resulting crystal was filtered to obtain Exemplary Compound 101 (4.11 g).

  As described above, the synthesis example of the exemplary compound 101 has been described as a synthesis example of the polymerizable group-containing dye multimer, but other polymerizable group-containing dye multimers are also synthesized from the chemical viewpoint by a method according to the above synthesis example. Can be synthesized.

[Examples 1-8, Comparative Examples 1-2]
<Preparation of colored curable composition>
The following components were mixed and dissolved to obtain a colored composition 1 which is a colored curable composition.

Pigment Blue-15: 6 dispersion (solid concentration 15%, pigment concentration 11.54%) 55.47 parts Dye (Exemplary Compound 101 of the dye multimer) 3.20 parts Polymerizable monomer ( KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) ... 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 (CW-1, manufactured by Zeneca) 1% CyH Solution: 0.1 part propylene glycol monomethyl ether acetate (PGMEA)
... 34.79 parts

  Next, colored compositions 2 to 10 which were colored curable compositions were prepared in the same manner as the colored composition 1 except that the types and amounts of the components were changed as shown in Table 2 below.

For each component in Table 2, the numerical value in parentheses represents the ratio (% by mass) of each component in the colored composition.
In Table 2, “PGME” represents propylene glycol monomethyl ether, “PB15: 6” represents Pigment Blue-15: 6, and “PV23” represents Pigment Violet23.
The “PB15: 6 dispersion” in the colored compositions 2 to 5 and 7 to 10 is the same as the “PB15: 6 dispersion” in the colored composition 1.
Moreover, mass ratio [PV23 / PB15: 6] in the “dispersion liquid of PB15: 6 and PV23” used for the coloring composition 6 is 8.0 / 1.0.
The structures of initiator 1 to initiator 3, monomer 1 to monomer 3, comparative dye A, and comparative dye B in the photopolymerization initiator column in Table 2 are shown below.

<Production of monochromatic color filter and evaluation of color blur>
(1) Production of silicon wafer with undercoat layer A 6-inch silicon wafer 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 the silicon wafer 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 silicon wafer with an undercoat layer was obtained.

(2) Application, exposure and development of colored curable composition The colored curable composition (colored compositions 1 to 10) was applied on the undercoat layer of the silicon wafer with an undercoat layer obtained in (1) above. A photocurable 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 silicon wafer 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), and CD-2000 (Fuji Film Electronics). Paddle development was performed at 23 ° C. for 60 seconds using Materials Co., Ltd. Next, while rotating the silicon wafer at a rotation speed of 50 rpm, pure water was supplied from the upper part of the rotation center in a shower shape to perform a rinsing treatment, 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 apparatus (UMA-802-HC552FFAL: manufactured by Ushio Electric Co., Ltd.). Thereafter, the colored pattern was cured by heating at 200 ° C. for 300 seconds.
Thus, a silicon wafer with a colored pattern (blue single color filter) was obtained.

(4) Preparation of transparent film composition solution The components of the following composition were mixed and dissolved to prepare a transparent film composition solution (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 (4) above to the colored pattern forming surface side of the silicon wafer with a colored pattern obtained in (3) above, 100 Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 0 ° C.

(6) Post-curing treatment of transparent film composition UV irradiation apparatus UMA-802-HC552FFAL (manufactured by Ushio Electric Co., Ltd.) was used on the wafer coated with the transparent film composition, and 350 mW / cm ² was applied for 30 sec at 35 ° C. Irradiated. Thereafter, the silicon wafer on which the irradiated coating film was formed was subjected to heat treatment at 200 ° C. for 300 seconds.
As described above, a transparent film was formed on the colored pattern forming surface side of the silicon wafer with the colored pattern.

(7) Evaluation The 10.0 μm square colored pattern (Bayer pattern) obtained as described above, which is protected by a transparent film, is observed 500 times with an optical microscope from directly above the pattern, and the transparent film from the pattern edge. Whether the dye was exuded or not was evaluated according to the following criteria. The evaluation results are shown in Table 3 below.

-Criteria-
A: No bleeding is observed, or the bleeding range is less than 1.0 μm from the pattern edge.
Δ: Bleeding is observed in the range from 1.0 μm to 5.0 μm from the pattern edge.
X: Bleeding is observed in a range exceeding 5.0 μm from the pattern edge.

  As shown in Table 3, in Examples 1 to 8 in which a coloring pattern was formed using a coloring composition 1 to 8 including a phthalocyanine pigment, a polymerizable group and a group derived from a dipyrromethene dye, Color bleeding was suppressed. On the other hand, in Comparative Examples 1 and 2 in which a colored pattern was formed using the colored compositions 9 and 10 containing a dye other than the pigment multimer, color bleeding was deteriorated.

  In the above embodiment, a 10 μm square colored pattern is formed. However, when a fine colored pattern (for example, 1.0 μm square) is formed, the color blur is suppressed as in the above embodiment.

  As described above, as examples 1 to 8, examples of forming a blue coloring pattern (color filter) on a silicon wafer substrate using the coloring compositions 1 to 8 have been described. On a silicon wafer substrate on which an image sensor is formed), a blue color filter is formed using the colored compositions 1 to 8, a green color filter is formed by a known method using a green color resist, and a red color resist is used. By producing red color filters by the above method, three color filters can be produced on a silicon wafer on which devices have been formed. The solid-state imaging device including these three color filters has excellent color reproducibility because color bleeding in the blue color filter is suppressed.

Claims (10)

  A colored curable composition comprising a phthalocyanine pigment, a dye multimer comprising a polymerizable group and a group derived from a dipyrromethene dye, a polymerization initiator, a polymerizable compound, and a solvent.   The colored curable composition according to claim 1, wherein the dye multimer includes a structural unit having a polymerizable group and a structural unit having a group derived from a dipyrromethene dye as repeating units.   The colored curable composition according to claim 1 or 2, wherein the polymerizable group is an ethylenically unsaturated group. The colored curable composition according to any one of claims 1 to 3, wherein the dipyrromethene dye is a dipyrromethene dye represented by the following general formula (C).


[In General Formula (C), R ^{2 to} R ⁵ each independently represent a hydrogen atom or a substituent, and 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. X ³ and X ⁴ each independently represent NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, Or represents a sulfur atom. Y ¹ represents NRc (Rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), or a nitrogen atom. Y ² represents a nitrogen atom or a carbon atom. R ⁸ and R ⁹ each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁸ and Y ¹ may be bonded to each other to form a 5-, 6-, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1, or 2. ]   The colored curable composition according to any one of claims 1 to 4, further comprising a dioxazine pigment.   The dioxazine pigment is C.I. I. The colored curable composition according to claim 5, which is CI Pigment Violet 23.   The colored curable composition according to any one of claims 1 to 6, wherein the polymerization initiator is an oxime photopolymerization initiator.   The color filter which uses the colored curable composition of any one of Claims 1-7. A step (A) of forming a colored curable composition layer by applying the colored curable composition according to any one of claims 1 to 7 on a support;
A step (B) in which the colored curable composition layer formed in the step (A) is exposed through a mask and then developed to form a colored pattern;
The manufacturing method of the color filter which has this.   A solid-state imaging device comprising the color filter according to claim 8.