WO2012108435A1 - Colored curable composition, and color filter - Google Patents

Abstract

A colored curable composition having high color purity and superior transmissivity is provided. The colored curable composition is soluble in an organic solvent, with main absorption in the range of 680-800 nm in a chloroform solvent, and contains a phthalocyanine compound having a substructure comprising at least one of a chlorine atom and a bromine atom, as well as one or more substituents represented by general formula (1), on the same benzene nucleus. (In general formula (1), X¹ represents an oxygen atom, a sulfur atom, an SO₂ group, or an NH group; and R¹ represents an alkyl group or an aryl group.)

Description

Colored curable composition and color filter

The present invention relates to a colored curable composition and a color filter using the colored curable composition. Furthermore, the present invention relates to a liquid crystal display device and a solid-state imaging device using the color filter. Moreover, it is related with the manufacturing method of a color filter.

Conventionally, color filters are colored curable compositions by containing a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed, a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components as necessary. It is manufactured by forming a colored pattern by using a photolithography method, an ink jet method or the like.

In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. Similarly, color filters for image sensors (solid-state imaging devices) are required to further improve color characteristics such as reduction of color unevenness and improvement of color resolution.

However, in the conventional pigment dispersion system, problems such as the occurrence of scattering due to coarse particles of pigment and the increase in viscosity due to poor dispersion stability tend to occur, and it is often difficult to further improve the contrast and brightness.

Therefore, conventionally, as a colorant, it has been studied to use not only a pigment but also a dye (for example, see Patent Document 1). When a dye is used as a colorant, the hue and brightness of a display image when an image is displayed can be increased due to the color purity of the dye itself and the vividness of the hue, and contrast can be improved because coarse particles are eliminated. It is useful in terms.

As examples of dyes, compounds having a wide variety of pigment bases such as phthalocyanine dyes, dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes are known (see, for example, Patent Documents 2 to 6).

JP-A-6-75375 JP 2008-292970 A JP 2007-039478 A JP-A-9-157536 JP-A-6-51115 JP-A-11-152415

Here, the colored curable composition used for a color filter or the like is required to have high color purity and no absorption (high transmittance) in an unnecessary part as a color filter. In addition, high light resistance is also required. The present invention aims to reconcile these two problems, and is a colored curable composition that can produce a color filter that does not have absorption in unnecessary portions as a color filter and has high light resistance. The purpose is to provide. In particular, it is an object to provide a useful thing as a colored material for a green filter.

Under such circumstances, the inventors of the present application have conducted intensive studies, and as a result, by forming an H-aggregate of a phthalocyanine compound having a main absorption in chloroform of 680 to 800 nm, the absorption position is shortened. It has been found that by shifting to the wavelength side (for example, 640 to 680 nm), a curable composition for coloring can be obtained which has no absorption in a portion unnecessary as a color filter and has high light resistance. In particular, it has been found useful as a coloring curable composition for green, and the present invention has been completed.

（一般式（１）中Ｘ¹は酸素原子、硫黄原子、ＳＯ₂基またはＮＨ基を表し、Ｒ¹は、アルキル基またはアリール基を表す。）
＜２＞前記フタロシアニン化合物が下記一般式（２）で表される、＜１＞に記載の着色硬化性組成物。

（一般式（２）中、ＭはＣｕ、Ｚｎ、Ｖ（＝Ｏ）、Ｍｇ、Ｎｉ、Ｔｉ（＝Ｏ）、Ｍｇ、ＳｎまたはＳｉを表す。Ａ、Ｂ、ＣおよびＤの少なくとも１つは、下記一般式（３）で表される構造を有し、他は芳香族環を示す。）

（一般式（３）中のＸａは、塩素原子もしくは臭素原子を表し、Ｒ²、Ｒ³およびＲ⁴の少なくとも１つは一般式（１）の基を表し、残りは水素原子もしくは、塩素原子、臭素原子である。）
＜３＞Ｍが、Ｃｕ、ＺｎまたはＶ（＝Ｏ）である、＜１＞または＜２＞に記載の着色硬化性組成物。
＜４＞一般式（１）におけるＡ、Ｂ、ＣおよびＤが、それぞれ、一般式（３）で表される、＜２＞または＜３＞に記載の着色硬化性組成物。
＜５＞一般式（１）におけるＡ、Ｂ、ＣおよびＤが、同一の一般式（３）で表される、＜２＞または＜３＞に記載の着色硬化性組成物。
＜６＞Ｒ²およびＲ³の一方が一般式（１）の基を表し、Ｒ²、Ｒ³およびＲ⁴の残りは水素原子、塩素原子または臭素原子である、＜２＞または＜３＞に記載の着色硬化性組成物。
＜７＞さらに、重合性化合物と光重合開始剤とを含有する、＜１＞～＜６＞のいずれかに記載の着色硬化性組成物。
＜８＞光重合開始剤がオキシム化合物またはビイミダゾール系化合物である＜７＞に記載の着色硬化性組成物。
＜９＞さらに黄色着色剤を含む、＜１＞～＜８＞のいずれかに記載の着色硬化性組成物。
＜１０＞黄色着色剤がアゾ系染料もしくはモノメチン系染料である＜９＞に記載の着色硬化性組成物。
＜１１＞黄色着色剤が下記一般式（４）で表されるモノメチン染料である＜１０＞に記載の着色硬化性組成物。

（一般式（４）中、Ｒ¹¹はアルキル基を表し、Ｒ¹²は置換基を有する芳香族環基を表す。）
＜１２＞＜１＞～＜１１＞のいずれかに記載の着色硬化性組成物を用いた着色層を有するカラーフィルタ。
＜１３＞＜１＞～＜１１＞のいずれかに記載の着色硬化性組成物を基板上に適用し、着色層を形成する工程と、形成された前記着色層をパターン状に露光し、現像して着色領域を形成する工程と、を有するカラーフィルタの製造方法。
＜１４＞＜１２＞に記載のカラーフィルタ、又は＜１３＞に記載のカラーフィルタの製造方法により作製されたカラーフィルタを有する液晶表示装置または固体撮像素子。
＜１５＞下記Ａ－１～Ａ－２４の何れかの化合物。

Specifically, the above problem has been solved by the following means.
<1> Soluble in an organic solvent, and the main absorption in a chloroform solvent is in the range of 680 nm to 800 nm. The same benzene nucleus is represented by the following general formula (1) and at least one of a chlorine atom and a bromine atom. A colored curable composition containing a phthalocyanine compound having a partial structure having one or more substitutions.

(In the general formula (1), X ¹ represents an oxygen atom, a sulfur atom, an SO ₂ group or an NH group, and R ¹ represents an alkyl group or an aryl group.)
<2> The colored curable composition according to <1>, wherein the phthalocyanine compound is represented by the following general formula (2).

(In the general formula (2), M represents Cu, Zn, V (═O), Mg, Ni, Ti (═O), Mg, Sn, or Si. At least one of A, B, C, and D represents And has a structure represented by the following general formula (3), and the others represent aromatic rings.)

(Xa in the general formula (3) represents a chlorine atom or a bromine atom, at least one of R ^2, R ³ and R ⁴ represents a group of the general formula (1), the rest or hydrogen atom, a chlorine atom A bromine atom.)
<3> The colored curable composition according to <1> or <2>, wherein M is Cu, Zn, or V (═O).
<4> The colored curable composition according to <2> or <3>, wherein A, B, C and D in the general formula (1) are each represented by the general formula (3).
<5> The colored curable composition according to <2> or <3>, wherein A, B, C and D in the general formula (1) are represented by the same general formula (3).
<6> One of R ² and R ³ represents a group of the general formula (1), and the remainder of R ² , R ³ and R ⁴ is a hydrogen atom, a chlorine atom or a bromine atom, <2> or <3> The colored curable composition described in 1.
<7> The colored curable composition according to any one of <1> to <6>, further comprising a polymerizable compound and a photopolymerization initiator.
<8> The colored curable composition according to <7>, wherein the photopolymerization initiator is an oxime compound or a biimidazole compound.
<9> The colored curable composition according to any one of <1> to <8>, further comprising a yellow colorant.
<10> The colored curable composition according to <9>, wherein the yellow colorant is an azo dye or a monomethine dye.
<11> The colored curable composition according to <10>, wherein the yellow colorant is a monomethine dye represented by the following general formula (4).

(In General Formula (4), R ¹¹ represents an alkyl group, and R ¹² represents an aromatic ring group having a substituent.)
<12> A color filter having a colored layer using the colored curable composition according to any one of <1> to <11>.
<13> Applying the colored curable composition according to any one of <1> to <11> on a substrate to form a colored layer, exposing the formed colored layer in a pattern, and developing And a step of forming a colored region.
<14> A liquid crystal display device or a solid-state imaging device having a color filter according to <12> or a color filter produced by the method for producing a color filter according to <13>.
<15> A compound of any one of A-1 to A-24 below.

According to the present invention, it is possible to provide a colored curable composition having high color purity and having no absorption in a portion unnecessary as a color filter (high transmittance). Therefore, it can be preferably used as a color filter, particularly as a green color filter. Furthermore, according to the present invention, it is possible to provide a liquid crystal display device and a solid-state imaging device in which the display image is vividly colored and exhibits high contrast.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified.

（一般式（１）中Ｘ¹は酸素原子、硫黄原子、ＳＯ₂基またはＮＨ基を表し、Ｒ¹は、アルキル基またはアリール基を表す。）
　本発明で用いるフタロシアニン化合物は、分子間相互作用が強まる状態におかれると、Ｈ会合体を形成し、吸収極大が短波長側（例えば、６４０～６８０ｎｍ）にシフトする。そして、短波吸収側のスソ引きに優れ、すなわち、急峻な立ち上がりを示すスペクトルを有することになる。この結果、本発明では、色純度が高く、カラーフィルタとして不必要な部分に吸収を有さない（透過率の高い）着色硬化性組成物を提供することができる。さらに、黄色着色剤との組み合わせで、グリーン用カラーフィルタに優れた着色硬化性組成物が得られる。
　ここで、主吸収とは、該フタロシアニン化合物の極大吸収のうち、最も大きな吸収をいう。本発明では、主吸収は、７００～７８０ｎｍであることが好ましく、７００～７６０ｎｍであることがより好ましい。
　フタロシアニン化合物をカラーフィルタの着色物として使用する検討は多数されている（特許第３４７６２０８）が、特にグリーンフィルタ用の着色物として満足する色純度と透過率を両立する着色物は得られていない。かかる観点から、本発明の意義は大きい。
　また、本発明で用いるフタロシアニン化合物は、５５０ｎｍにおける吸収強度と６５０ｎｍにおける吸収強度の比（５５０ｎｍ／６５０ｎｍ）が０～０．１の範囲にあることが好ましく、０～０．２の範囲にあることがさらに好ましい。 <Colored curable composition>
The colored curable composition of the present invention is soluble in an organic solvent, has a main absorption in a chloroform solvent in the range of 700 nm to 800 nm, has at least one of a chlorine atom and a bromine atom, and It contains a phthalocyanine compound having a partial structure having one or more substitutions represented by the general formula (1).

(In the general formula (1), X ¹ represents an oxygen atom, a sulfur atom, an SO ₂ group or an NH group, and R ¹ represents an alkyl group or an aryl group.)
When the phthalocyanine compound used in the present invention is placed in a state where the intermolecular interaction is strengthened, an H-aggregate is formed and the absorption maximum is shifted to the short wavelength side (for example, 640 to 680 nm). And it is excellent in the pulling on the short wave absorption side, that is, has a spectrum showing a steep rise. As a result, according to the present invention, it is possible to provide a colored curable composition having high color purity and having no absorption (high transmittance) in an unnecessary portion as a color filter. Furthermore, a colored curable composition excellent in a color filter for green can be obtained in combination with a yellow colorant.
Here, the main absorption refers to the largest absorption among the maximum absorptions of the phthalocyanine compound. In the present invention, the main absorption is preferably 700 to 780 nm, and more preferably 700 to 760 nm.
Many studies have been made on the use of phthalocyanine compounds as color filters (Japanese Patent No. 3476208), but no color products that satisfy both color purity and transmittance, which are particularly satisfactory as color products for green filters, have not been obtained. From this viewpoint, the significance of the present invention is great.
In the phthalocyanine compound used in the present invention, the ratio of the absorption intensity at 550 nm to the absorption intensity at 650 nm (550 nm / 650 nm) is preferably in the range of 0 to 0.1, and preferably in the range of 0 to 0.2. Is more preferable.

In the general formula (1), X ¹ represents an oxygen atom, sulfur atom, SO ₂ group or NH group, preferably an oxygen atom, SO ₂ group or NH group, and more preferably an oxygen atom or SO ₂ group. When sulfur atoms are used, the soret band absorption becomes long wave, the absorption intensity at 550 nm increases, and the absorption intensity ratio (contrast) tends to be inferior.

In general formula (1), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent. More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. Examples of the substituent substituted on the alkyl group include a halogen atom, an alkyloxy group, an aryloxy group, an aminosulfonyl group, a sulfamoyl group, an alkoxycarbonyl group, and a carbamoyl group. Such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, Cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group, phenoxyethyl group, benzyl group, phenylethyl group, N-butylaminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonyl And a propyl group, an ethoxyethoxyethyl group, and a 2-chloroethyl group, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a phenoxyethyl group, a benzyl group, a phenylethyl group, and an N-butylaminosulfonyl group. Propyl group, N And butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group, and ethoxyethoxyethyl group. Particularly preferred are methyl group, ethyl group, propyl group, butyl group, phenoxyethyl group, benzyl group, phenylethyl group, Examples thereof include N-butylaminosulfonylpropyl group, N-butylaminocarbonylmethyl group, N, N-dibutylaminosulfonylpropyl group, and ethoxyethoxyethyl group.

In the general formula (1), the aryl group represented by R ^1, may have a substituent preferably an aryl group having 6 to 30 carbon atoms. More preferably, it has 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Examples of the substituent substituted on the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aminosulfonyl group, an aminocarbonyl group, and an alkoxycarbonyl group. Such aryl groups include phenyl, 2-chlorophenyl, 2-methoxyphenyl, 4-butoxycarbonylphenyl, 4-N, N-dibutylaminocarbonylphenyl, 4-N-butylaminosulfonylphenyl More preferred are phenyl group, 4-butoxycarbonylphenyl group, 4-N, N-dibutylaminocarbonylphenyl group, 4-N-butylaminosulfonylphenyl group, and particularly preferred are phenyl group, 4- Examples include butoxycarbonylphenyl group and 4-N, N-dibutylaminocarbonylphenyl group.

（一般式（２）中、ＭはＣｕ、Ｚｎ、Ｖ（＝Ｏ）、Ｍｇ、Ｎｉ、Ｔｉ（＝Ｏ）、Ｍｇ、ＳｎまたはＳｉを表す。Ａ、Ｂ、ＣおよびＤの少なくとも１つは、下記一般式（３）で表される構造を有し、他は芳香族環を示す。）

（一般式（３）中のＸａは、塩素原子もしくは臭素原子を表し、Ｒ²、Ｒ³およびＲ⁴の少なくとも１つは一般式（１）の基を表し、残りは水素原子もしくは、塩素原子、臭素原子である。） The phthalocyanine compound used in the present invention is preferably a compound represented by the following general formula (2).

(In the general formula (2), M represents Cu, Zn, V (═O), Mg, Ni, Ti (═O), Mg, Sn, or Si. At least one of A, B, C, and D represents And has a structure represented by the following general formula (3), and the others represent aromatic rings.)

(Xa in the general formula (3) represents a chlorine atom or a bromine atom, at least one of R ^2, R ³ and R ⁴ represents a group of the general formula (1), the rest or hydrogen atom, a chlorine atom A bromine atom.)

M is preferably Cu, Zn, V = O.

At least one of A, B, C and D has a structure represented by the following general formula (3), and the other is an aromatic ring. The other aromatic ring is preferably a benzene ring. A, B, C and D are each more preferably represented by the general formula (3), and more preferably the same general formula (3). By adopting the same structure, the absorption on the short-wave side of the main absorption is sharpened, and the absorption intensity ratio (contrast) is easily improved.

In general formula (2), as a halogen atom represented by R < ² >, R < ³ >, R < ⁴ >, a chloro atom or a bromine atom is respectively preferable.
In the general formula (2), one of R ² , R ³ and R ⁴ represents the group of the general formula (1), and the rest is preferably a hydrogen atom, a chlorine atom or a bromine atom. In the present invention, it is particularly preferable that one of R ² and R ³ represents the group of the general formula (1), and the remainder of R ² , R ³ and R ⁴ is a hydrogen atom, a chlorine atom or a bromine atom. By adopting this configuration, the association formation of phthalocyanine is promoted, and the absorption intensity ratio (contrast) is easily improved.

（一般式（２－２）中、ＭはＣｕまたはＺｎ、を表す。Ｘａは塩素原子または臭素原子を表す。Ｘｂは水素原子、塩素原子または臭素原子を表す。Ｘ¹およびＲ¹は一般式（１）と同一であり、好ましい範囲も同義である。） The phthalocyanine compound used in the present invention is more preferably a compound represented by the general formula (2-2). By adopting a compound in such a range, the effects of the present invention tend to be exhibited more effectively.
Formula (2-2)

(In the general formula (2-2), M represents Cu or Zn. Xa represents a chlorine atom or a bromine atom. Xb represents a hydrogen atom, a chlorine atom or a bromine atom. X ¹ and R ¹ represent the general formula. (It is the same as (1), and the preferred range is also synonymous.)

Although the example of the phthalocyanine compound used by this invention is given to the following, it cannot be overemphasized that this invention is not limited to these.

The above-mentioned phthalocyanine compound can be synthesized according to the methods described in “Phthalocyanine as a functional dye, issued by IPC”, “Phthalocyanine—Chemistry and Function,” issued by IPC, etc.

The content of the phthalocyanine compound in the colored curable composition varies depending on the molecular weight and its extinction coefficient, but is preferably 1 to 70% by mass with respect to the total solid content of the colored curable composition, and is 10 to 50% by mass. % Is more preferable. When the dye content is 10% by mass or more, a good color density (for example, a color density suitable for liquid crystal display) can be obtained, and when it is 50% by mass or less, pixel patterning becomes good. Is advantageous.

[Coloring compounds]
Further, the colored curable composition of the present invention may contain dye compounds and pigment compounds having other structures and dispersions thereof. The dye compound may have any structure as long as it does not affect the hue of the colored image. For example, azo (for example, Solvent Yellow 162), anthraquinone (for example, JP-A-2001-10881). Anthraquinone compounds), phthalocyanine compounds (for example, phthalocyanine compounds described in US Patent 2008 / 0076044A1), xanthene compounds (for example, CI Acid. Red 289), triarylmethanes Series (for example, CI Acid Blue 7), CI Acid Blue 83, CI Acid Blue 90, CI Solvent Blue 38 (CISolvent Blue38), CI Acid Violet 17, Over Eye Acid Violet 49 (CIAcid Violet49), CI Acid Green 3 (CIAcid Green3), methine dyes, monomethine dye (CIsolvent / yellow93)
Etc.

Examples of pigment compounds include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triarylcarbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, Indigo, thioindigo, isoindoline, isoindolinone, pyranthrone, isoviolanthrone and the like. More specifically, for example, perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, perinone compound pigments such as Pigment Orange 43, and Pigment Red 194, Pigment Violet 19, and Pigment Violet. 42, quinacridone such as pigment red 122, pigment red 192, pigment red 202, pigment red 207, or pigment red 209 quinacridone compound pigment, pigment red 206, pigment orange 48, or pigment orange 49 Quinone compound pigments, anthraquinone compound pigments such as pigment yellow 147, anthanthrone compound pigments such as pigment red 168, and pigments Benzimidazolone compound pigments such as Pigment 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185 Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, Pigment Red Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, or Pigment Red Disazo condensation compound pigments such as Rune 23, pigment yellow 13, pigment yellow 83, or disazo compound pigments such as pigment yellow 188, pigment red 187, pigment red 170, pigment yellow 74, pigment yellow 150, Pigment Red 48, Pigment Red 53, Pigment Orange 64, Pigment Red 247 and other azo compound pigments, Pigment Blue 60 and other indanthrone compound pigments, Pigment Green 7, Pigment Green 36, Pigment Green 37, phthalocyanine compound pigments such as Pigment Green 58, Pigment Blue 16, Pigment Blue 75, or Pigment Blue 15, Pigment Blue 56, Alternatively, a triarylcarbonium compound pigment such as Pigment Blue 61, a dioxazine compound pigment such as Pigment Violet 23, or Pigment Violet 37, an anthraquinone compound pigment such as Pigment Red 177, Pigment Red 254, and Pigment Red 255 Pigment Red 264, Pigment Red 272, Pigment Orange 71, or Pigment Orange 73, etc., Diketopyrrolopyrrole Compound Pigment, Pigment Red 88 or other thioindigo compound pigment, Pigment Yellow 139, Pigment Orange 66, etc. Isoindoline compound pigments such as Pigment Yellow 109, Pigment Orange 61, and Pigment Orange 61 0 or pyranthrone compound pigments such as Pigment Red 216 or isoviolanthrone compound pigments, such as Pigment Violet 31, and the like.

In the present invention, the colorant is preferably a yellow colorant, more preferably pigment yellow 150 or pigment yellow 139, and a preferred dye is C.I. I. Solvent Yellow 4, C.I. I. Solvent Yellow 88, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 94, C.I. I. Solvent Yellow 98, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 82, C.I. I. Solvent Yellow 93.

（一般式（４）中、Ｒ¹¹はアルキル基を表し、Ｒ¹²は置換基を有する芳香族環基を表す。）
　Ｒ¹¹は炭素数１～１２のアルキル基が好ましく、１～６のアルキル基がより好ましい。Ｒ¹²は、フェニル基、ナフチル基が好ましく、置換基としては、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルカルボニルアミノ基、アリールカルボニルアミノ基が好ましく、特にアルキルスルホニルアミノ基が好ましい。 In the present invention, the yellow colorant is preferably a monomethine dye, and the yellow colorant is more preferably a monomethine dye represented by the following general formula (4).

(In General Formula (4), R ¹¹ represents an alkyl group, and R ¹² represents an aromatic ring group having a substituent.)
R ¹¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. R ¹² is preferably a phenyl group or a naphthyl group, and the substituent is preferably an alkylsulfonylamino group, an arylsulfonylamino group, an alkylcarbonylamino group or an arylcarbonylamino group, particularly preferably an alkylsulfonylamino group.

When the dye or pigment is blended as a dispersion, it can be adjusted according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.
The content of the dye or pigment can be used within a range that does not impair the effects of the present invention, and is 0.5% by mass to 70% by mass with respect to the total solid content of the colored curable composition of the present invention. preferable. Further, it is preferably added to the colored curable composition so that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05.

[Polymerizable compound]
The colored curable composition of the present invention preferably contains at least one 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.

Examples of monomers and their (co) polymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, 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 these (co) polymers 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.

Specific examples of an ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetra Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol tria Relate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanur Examples include acid EO-modified triacrylate.
Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like.

Further, itaconic acid esters such as ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol Diitaconate, sorbitol tetritaconate, etc., and crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, etc. For example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. To, for example, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetra malate, and the like.
Examples of other esters include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

Also suitable are urethane-based addition-polymerizable compounds produced by the addition reaction of isocyanate and hydroxyl group. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. Vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Compounds and the like.
CH ₂ = C (R) COOCH ₂ CH (R ′) OH (A)
[In General Formula (A), R and R ′ each independently represent H or CH ₃ . ]

About these polymerizable compounds, the structure, details of usage such as single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the colored curable composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the colored cured film, those having three or more functions are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) are used in combination. Thus, a method of adjusting both sensitivity and intensity is also effective. In addition, the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the colored curable composition. The method of use is an important factor. For example, compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.

The content of the polymerizable compound in the total solid content of the colored curable composition (total content in the case of 2 or more types) is not particularly limited, and is 10 from the viewpoint of more effectively obtaining the effects of the present invention. % By mass to 80% by mass is preferable, 15% by mass to 75% by mass is more preferable, and 20% by mass to 60% by mass is particularly preferable.

[Photopolymerization initiator]
The colored curable composition of the present invention preferably contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.

Examples of the photopolymerization initiator include at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted 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, an oxime compound or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction.

The oxime compound (hereinafter also referred to as “oxime-based photopolymerization initiator”) is not particularly limited, and is described in, for example, JP-A No. 2000-80068, WO 02 / 100903A1, and JP-A No. 2001-233842. These oxime compounds are mentioned.
Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1, -Butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9- Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) 9H-carbazol-3-yl] ethanone, 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, 2- (acetoxyimino) -4- (4-chlorophenylthio) -1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1-butanone and the like. However, it is not limited to these.

In the present invention, the compound represented by the following general formula (1) is more preferable as the oxime compound from the viewpoints of sensitivity, time stability, and coloring during post-heating.

（一般式（１）中、ＲおよびＸは、それぞれ、１価の置換基を表し、Ａは、２価の有機基を表し、Ａｒは、アリール基を表す。ｎは、１～５の整数である。）

(In general formula (1), R and X each represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n represents an integer of 1 to 5. .)

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

A is an unsubstituted alkylene group, an alkylene group substituted with an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating, An alkylene group substituted with an alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, 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 the general formula (1), n is preferably an integer of 1 to 2.

The biimidazole compound is not limited in its structure as long as it is a dimer of an imidazole ring substituted with three aryl groups, and is particularly represented by the following general formula (II) or general formula (III). A compound having the structure is preferred.

In the general formula (II), X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms, and A represents 1 to 12 carbon atoms, respectively. A substituted or unsubstituted alkoxy group, or —COO—R ⁹ (wherein R ⁹ represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms), and n represents 1 to 3 And m is an integer of 1 to 3.

In general formula (III), X ¹ , X ² and X ³ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms. However, two or more of X ¹ , X ² and X ³ do not take a hydrogen atom at the same time.

Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4- Phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2 , 4-Dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichloro) Phenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5 ′ -Tetrakis (4-phenoxycarbonylphenyl) biimidazole,

2,2′-bis (2-cyanophenyl) -4,4 ′, 5.5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-cyanophenyl) -4,4 ', 5,5'-Tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5,5'-tetrakis (4-methoxycarbonylphenyl) biimidazole Imidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2-methylphenyl) -4 , 4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4 Methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis (2- Ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis ( 4-methoxycarbonylphenyl) biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) biimidazole, 2,2′-bis ( 2-Phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) biimidazole Things;

2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (p-methoxyphenyl) bisimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (m-methoxyphenyl) bisimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) bisimidazole 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra- (4-methoxyphenyl) bisimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′ , 5,5'-Tetra- (3-methoxyphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra- (3,4-dimethoxyphenyl) bis Imidazole

2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′ , 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2, 4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dicyanophenyl) -4,4 ′, 5,5′-tetra Phenylbiimidazole, 2,2'-bis (2,4,6-tricyanophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dimethylphenyl) ) -4,4 ', 5,5'-tetraphenylbiimi Sol, 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-diethylphenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (2,4-diphenylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4,6-triphenylphenyl) -4,4', 5 , 5′-tetraphenylbiimidazole, 2,2′-bis (2-fluorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole, 2,2′-bis (o-fluorophenyl)- 4,4 ', 5,5'-tetrapheny And the like biimidazole compound bis imidazole.

Among these, as a particularly preferable compound, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (commercially available products are B-CIM, manufactured by Hodogaya Chemical Co., Ltd.). 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (3,4-dimethoxyphenyl) biimidazole (HABI1311, Nippon Sebel Hegner), 2,2 Examples include '-bis (2-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole (commercially available from Kurokin Kasei Co., Ltd.).

In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph No. 0079 of JP-A No. 2004-295116 may be used in the colored curable composition of the present invention. 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 types) is 3% by mass to 20% by mass from the viewpoint of more effectively obtaining the effects of the present invention. %, More preferably 4% by mass to 19% by mass, and particularly preferably 5% by mass to 18% by mass.

[Organic solvent]
The colored curable composition of the present invention can contain at least one organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each of the coexisting components and the coating property when the colored curable composition is used, and in particular, the solubility of the binder, the coating property, It is preferable to select in consideration of safety.

Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. Oxyacetic acid alkyl esters (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate). )), 3-oxypropionic acid alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, 3-etho And 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (specifically, And methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), 2-oxy-2-methylpropion 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 Le, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

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

These organic solvents are preferably mixed in two or more types from the viewpoints of the solubility of each of the above-mentioned components and, when an alkali-soluble polymer is included, the solubility of the components and the improvement of the coated surface. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, 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 methyl ether, and propylene glycol methyl ether acetate.

The content of the organic 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, more preferably 15% by mass to 60% by mass. .

[Alkali-soluble binder]
The colored curable composition of the present invention preferably contains an alkali-soluble binder. 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 polymer, soluble in an organic solvent and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, 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 those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth)). 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 chain butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the above-mentioned polymer containing a polymerizable group include 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, etc. are also useful.

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

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by the GPC method) of 1000 to 2 × 10 ⁵ , and a weight of 2000 to 1 × 10 ⁵ in terms of developability and liquid viscosity. Polymers are more preferred, and polymers of 5000 to 5 × 10 ⁴ are particularly preferred.

The blending amount of the alkali-soluble binder is preferably 10 to 80% by mass, more preferably 20 to 60% by mass based on the total solid content.

[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, which is 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, reference can be made to the descriptions in paragraph numbers 0134 to 0147 of JP-A No. 2004-295116.

[Surfactant]
The colored curable composition of the present invention may contain a surfactant. The surfactant may be any of nonionic, cationic, or anionic, and a fluorine-containing surfactant is preferable. Specifically, JP-A-2-54202 is exemplified.
The blending amount of the surfactant in the present invention is preferably 0.0001 to% by mass of the total solid content.

The colored curable composition of the present invention may further contain various additives such as a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a sensitizer and a light stabilizer, as necessary.

[Method for preparing colored curable composition]
The colored curable composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
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 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 form a colored cured film excellent in hue and contrast, a color filter used in a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.) It can be suitably used for forming colored pixels such as printing inks, inkjet inks, and paints. In particular, it is suitable for use in forming colored pixels for liquid crystal display devices.

[Color filter and manufacturing method thereof]
The color filter of the present invention is configured by providing a substrate and a colored region containing the colored curable composition of the present invention on the substrate. The colored region on the substrate is composed of colored films such as red (R), green (G), and blue (B) that form each pixel of the color filter.

The color filter of the present invention may be formed by any method as long as it can form a colored region (colored pattern) cured by applying the colored curable composition of the present invention onto a substrate. Preferably, it is produced using the colored curable composition of the present invention.

In the method for producing a color filter of the present invention, the above-described colored curable composition is applied (preferably applied) on a substrate to form a colored layer (also referred to as a colored curable composition layer) (A And a step (B) of curing the colored curable composition layer formed in the step (A).
The curing step is preferably performed in a pattern (preferably through a mask), and the uncured portion of the coating film is developed and removed with a developer to form a colored region (colored pattern). By passing through these steps, a colored pattern composed of pixels of each color (3 colors or 4 colors) is formed, and a color filter can be obtained. 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) are applied. On the other hand, the aspect which further provided the process (D) which heat-processes is preferable.
By such a method, a color filter used for a liquid crystal display element or a solid-state imaging element can be manufactured with low process difficulty, high quality, and low cost.
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 above-described colored curable composition of the present invention is applied on a substrate directly or via another layer by a desired coating method, and then the colored curable composition is coated. A coating film (colored curable composition layer) is formed, and then pre-cured (prebaked) as necessary, and the colored curable composition layer is dried.

As the substrate, for example, alkali-free glass, sodium glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film thereto, solid-state imaging elements, and the like are used. Examples of the photoelectric conversion element substrate include a silicone substrate and a plastic substrate. On these substrates, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion. Further, if necessary, an undercoat layer may be provided on the substrate in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

In addition, a driving substrate on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed (hereinafter referred to as “TFT type liquid crystal driving substrate”) is used as the substrate. Furthermore, a color pattern formed using the colored curable composition of the present invention can be formed to produce a color filter.
Examples of the substrate in the TFT type liquid crystal driving substrate include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of the TFT liquid crystal driving substrate can be used.

The colored curable composition of the present invention is applied to the substrate directly or via another layer. As a method to be applied, coating is preferable, and coating is preferably performed by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, and inkjet.

In the coating step, the method for applying the colored curable composition of the present invention to the substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter, Slit nozzle coating method) is preferable.
In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. In this case, the discharge amount of the colored curable composition from the slit nozzle is usually 500 microliters / second to 2000 microliters / second, preferably 800 microliters / second to 1500 microliters / second. The speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
The solid content of the colored curable composition used in the coating step is usually 10% to 20%, preferably 13% to 18%.

When forming a coating film of the colored curable composition of the present invention on a substrate, the thickness of the coating film (after pre-baking treatment) is generally 0.3 μm to 5.0 μm, preferably 0.5 μm to 4 μm. It is 0.0 μm, and most desirably 0.5 μm to 3.0 μm.
In the case of a color filter for a solid-state image sensor, the thickness of the coating film (after pre-baking) is preferably in the range of 0.5 μm to 5.0 μm.

In the application process, usually, a pre-bake treatment is performed after application. If necessary, vacuum treatment can be performed before pre-baking. The vacuum drying conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed in a temperature range of 50 ° C. to 140 ° C., preferably about 70 ° C. to 110 ° C., using a hot plate, an oven, etc., and can be performed under conditions of 10 seconds to 300 seconds. Note that high-frequency treatment or the like may be used in combination with the pre-bake treatment. The high frequency treatment can be used alone.

Examples of the pre-baking condition include a condition of heating at 70 to 130 ° C. for about 0.5 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 according to the purpose. In the color filter for a liquid crystal display device, the range of 0.2 μm to 5.0 μm is preferable, the range of 1.0 μm to 4.0 μm is more preferable, and the range of 1.5 μm to 3.5 μm is most preferable. In the color filter for a solid-state imaging device, the range of 0.2 μm to 5.0 μm is preferable, the range of 0.3 μm to 2.5 μm is more preferable, and the range of 0.3 μm to 1.5 μm is most preferable.
In addition, the thickness of the colored curable composition layer is a film thickness after pre-baking.

-Process (B)-
Subsequently, in the method for producing a color filter of the present invention, the film (colored curable composition layer) formed of the colored curable composition formed on the substrate as described above is exposed through, for example, a photomask. Is done. As light or radiation applicable to exposure, g-line, h-line, i-line, j-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, 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 a laser light source In an exposure method using a laser light source, an ultraviolet laser is used as the light source.
The irradiation light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 380 nm, more preferably an ultraviolet laser having a wavelength in the range of 300 nm to 360 nm matches the photosensitive wavelength of the resist. Is preferable. 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 of the object to be exposed (pattern) is in the range of 1 mJ / cm ² to 100 mJ / cm ² , and more preferably in the range of 1 mJ / cm ² to 50 mJ / cm ² . An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), DF2200G (Dainippon Screen) can be used. It is. Further, devices other than those described above are also preferably used.
When manufacturing a color filter for a liquid crystal display device, exposure using mainly h-line and i-line is preferably used by a proximity exposure machine and a mirror projection exposure machine. Further, when manufacturing a color filter for a solid-state image sensor, it is preferable to mainly use i-line in a stepper exposure machine. When manufacturing a color filter using a TFT type liquid crystal driving substrate, the photomask used has a through hole or a U-shaped depression in addition to a pattern for forming a pixel (colored pattern). The thing in which the pattern for forming is provided is used.

The colored curable composition layer exposed as described above can be heated.
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 exposure is developed with a developer. Thereby, a negative type or positive type coloring pattern (resist pattern) can be formed. In the development step, the uncured portion of the coating film after exposure is eluted in the developer, and only the cured portion remains on the substrate.
Any developer can be used as long as it dissolves the coating film (colored curable composition layer) of the colored curable composition in the uncured portion while not dissolving the cured portion. For example, combinations of various organic solvents and alkaline aqueous solutions can be used.
Examples of the organic solvent used for development include the above-described solvents that can be used when preparing the colored curable composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. An alkaline compound such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is used at a concentration of 0.001% by mass to 10% by mass, preferably 0.01%. Examples thereof include an alkaline aqueous solution dissolved so as to have a mass% to 1 mass%. 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.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 seconds to 90 seconds.
Development may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. It is also possible to prevent development unevenness by previously moistening the surface to be developed with water or the like before touching the developer. It is also possible to develop with the substrate tilted.
Further, when manufacturing a color filter for a solid-state image sensor, paddle development is also used.

After the development process, a rinsing process for washing and removing excess developer is performed, followed by drying, followed by heat treatment (post-baking) to complete the curing.
The rinsing process is usually performed with pure water, but in order to save liquid, pure water is used in the final cleaning, and used pure water is used in the initial stage of cleaning, or the substrate is inclined and cleaned. Alternatively, a method of using ultrasonic irradiation together may be used.

After the rinse treatment, after draining and drying, a heat treatment at about 200 ° C. to 250 ° C. is usually performed. In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with an expression.

By sequentially repeating the above steps for each color according to the desired number of hues, it is possible to produce a color filter in which a cured film (colored pattern) colored in a plurality of colors is formed.
Since the color filter of the present invention has high contrast, small color density unevenness, and good color characteristics, it can be suitably used for a solid-state imaging device or a liquid crystal display device.

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

-Process (D)-
It is preferable to further heat-treat the colored pattern that has been post-exposed by ultraviolet irradiation as described above. By heating the formed color pattern (so-called post-bake process), the color pattern can be further cured. This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
The temperature during the heat treatment is preferably 100 ° C. to 300 ° C., more preferably 150 ° C. to 250 ° C. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having a plurality of hue pixels, the above steps (A), (B), and if necessary, the steps (C) and (D) are repeated according to the desired number of colors. Good.
The process (C) and / or the process (D) may be performed every time the formation, exposure, and development of a monochromatic colored curable composition layer are completed (for each color), or a desired color. You may perform the said process (C) and / or a process (D) collectively after formation, exposure, and image development of all the colored curable composition layers of a number are complete | finished.

The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in hue and contrast since the colored curable composition of the present invention is used.
The color filter of the present invention can be used for a liquid crystal display element or a solid-state image sensor, and is particularly suitable for use in a liquid crystal display device. When used in a liquid crystal display device, it is possible to display an image excellent in spectral characteristics and contrast while achieving a good hue using a dye as a colorant.

As described above, the use of the colored curable composition of the present invention has been described mainly focusing on the formation of the color filter color pattern. However, the color curable composition of the present invention is used to form a black matrix that isolates the color pattern (pixels) constituting the color filter. Can also be applied.
The black matrix on the substrate is a colored curable composition containing a black pigment processed pigment such as carbon black, titanium black, etc., and is subjected to coating, exposure, and development steps. It can be formed by baking.

[Liquid Crystal Display]
The liquid crystal display element and the solid-state image sensor of the present invention are provided with the color filter of the present invention. More specifically, for example, by forming an alignment film on the inner surface side of the color filter, facing the electrode substrate, and filling the gap with liquid crystal and sealing, a panel which is the liquid crystal display element of the present invention is obtained. . For example, the solid-state image sensor of this invention is obtained by forming a color filter on a light receiving element.

For the definition of liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 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.)”. Further, 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 and 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.

When the color filter of the present invention is used for 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.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded. Unless otherwise specified, “part” is based on mass.

Synthesis of Exemplary Compound <A-3> C.I. Pigment Green 7 (2.3 parts by weight), 4-dibutylaminocarbonylthiophenol (2.2 parts by weight), potassium carbonate (2.3 parts by weight), NMP (20 parts by weight) of the mixed solution was stirred at 120 ° C. for 12 hours.
Ethyl acetate (50 parts by weight) and water (50 parts by weight) were added to the reaction solution, and the aqueous layer was neutralized with acetic acid.
The organic layer was separated, concentrated, and purified by silica gel chromatography to obtain 1.1 parts by weight of Exemplified Compound A-3.
The maximum absorption wavelength of the obtained compound in chloroform was 774 nm, and the molar extinction coefficient was 115000.
Although the substitution position of dibutylaminocarbonylthiophenol was substituted at the β-position of the benzene ring in the phthalocyanine ring, it was confirmed from the absorption change, but it was a mixture of isomers with different substitution positions. Hereinafter, the β-position introduction position of the substituent represented by the general formula (1) is a mixture of isomers having different substitution positions. Exemplified compounds A-1 to A-6 are all a mixture of isomers.

Synthesis of Exemplary Compound <A-1> m-Chloroperbenzoic acid (1.5 parts by weight) was added to a reaction solution of Exemplary Compound A-3 (1.0 parts by weight) and chloroform (20 parts by weight) at room temperature. For 3 hours.
Ethyl acetate (50 parts by weight) and water (50 parts by weight) were added to the reaction solution, and the organic layer was separated, concentrated, and purified by silica gel chromatography to obtain 0.8 parts by weight of Exemplified Compound A-1.
The maximum absorption wavelength of the obtained compound in chloroform was 730 nm, and the molar extinction coefficient was 100,000.

Synthesis of Exemplified Compound <A-2> Exemplified Compound <A-> except that 4-butylaminocarbonylphenol (2.0 parts by weight) was used instead of 4-dibutylaminocarbonylthiophenol (2.2 parts by weight) 3> was synthesized in the same manner as described above.
The maximum absorption wavelength of the obtained compound in chloroform was 752 nm, and the molar extinction coefficient was 110,000.

Synthesis of Exemplified Compound <A-5> Similar to Exemplified Compound A-3 except that n-dodecyl mercaptan (2.0 parts by weight) was used instead of 4-dibutylaminocarbonylthiophenol (2.2 parts by weight) The method was synthesized.
The maximum absorption wavelength of the obtained compound in chloroform was 740 nm, and the molar extinction coefficient was 115,000.

Synthesis of Exemplified Compound <A-4> Except that Exemplified Compound A-3 (1.0 part by weight) was changed to Exemplified Compound A-5 (1.0 part by weight), the same procedure as Exemplified Compound A-1 was used. Synthesized.
The maximum absorption wavelength of the obtained compound in chloroform was 725 nm, and the molar extinction coefficient was 105,000.

Synthesis of Exemplary Compound <A-6> C.I. Pigment Green 7 (2.3 parts by weight) was converted to C.I. Pigment Green 58 (2.6 parts by weight), dodecanol (1.5 parts by weight), tert- Butoxy potassium (1.5 parts by weight) and NMP (20 parts by weight) were reacted at 120 ° C. for 16 hours. Ethyl acetate (50 parts by weight) and water (50 parts by weight) were added to the reaction solution, and the aqueous layer was neutralized with acetic acid. The organic layer was separated, concentrated, and purified by silica gel chromatography to obtain 0.4 parts by weight of Exemplified Compound A-6.
The maximum absorption wavelength of the obtained compound in chloroform was 734 nm, and the molar extinction coefficient was 100,000.

Synthesis of Exemplary Compound <A-7> To a solution of tetrachlorophthalonitrile (26.6 parts by weight), dodecyl alcohol (19.0 parts by weight) and N-methylpyrrolidone (200 parts by weight), sodium hydride (60% Mineral oil, 4.0 parts by weight) was added. After stirring at room temperature for 3 hours, liquid separation was performed with ethyl acetate and 1N aqueous hydrochloric acid. The organic layer was concentrated and purified by silica gel chromatography.
Subsequently purified 4-dodecylalkoxy-substituted trichlorophthalonitrile (20 parts by weight), copper acetate (5.0 parts by weight), ammonium benzoate (8.0 parts by weight), 1-methoxy-2-propanol (500 parts by weight) ) Was reacted at 120 ° C. for 6 hours.
The reaction mixture was concentrated, extracted with chloroform and water, the organic layer was separated, concentrated, and purified by silica gel chromatography to give 10.2 parts by weight of Exemplified Compound A-7.
The maximum absorption wavelength of the obtained compound in chloroform was 708 nm, and the molar extinction coefficient was 130,000.
Theoretically, four types of cyclized isomers are included, but no data on the isomer formation ratio could be obtained. Exemplified compounds A-7 to A-24 are all a mixture of isomers.

<Exemplary Compound A-8>
Tetrachlorophthalonitrile (26.6 parts by weight), dodecyl mercaptan (20.2 parts by weight), potassium carbonate (20.0 parts by weight) and N-methylpyrrolidone (200 parts by weight) were reacted at 90 ° C. for 6 hours. It was. The reaction solution was extracted with ethyl acetate and 1N hydrochloric acid, and the organic layer was separated, concentrated, and purified by silica gel chromatography.
Subsequently, Exemplified Compound A-8 was synthesized from purified 4-dodecylthiotrichlorophthalonitrile in the same manner as Exemplified Compound A-7.
The maximum absorption wavelength of the obtained compound in chloroform was 722 nm, and the molar extinction coefficient was 140000.

<Exemplary Compound A-9>
Exemplified Compound A-9 was obtained by oxidizing Exemplified Compound A-8 in the same manner as Exemplified Compound A-1.
The maximum absorption wavelength of the obtained compound in chloroform was 728 nm, and the molar extinction coefficient was 135,000.

<Exemplary Compound A-10>
Exemplified compound A-10 was synthesized using dodecylamine instead of dodecyl mercaptan in the same manner as exemplified compound A-8.
The maximum absorption wavelength of the obtained compound in chloroform was 712 nm, and the molar extinction coefficient was 125,000.

<Exemplary Compound A-11>
Tetrachlorophthalonitrile (26.6 parts by weight), 2-isobutylphenol (15.6 parts by weight), potassium carbonate (20.0 parts by weight), N-methylpyrrolidone (200 parts by weight) at 90 ° C. for 6 hours Reacted. The reaction solution was extracted with ethyl acetate and 1N hydrochloric acid, and the organic layer was separated, concentrated, and purified by silica gel chromatography.
Subsequently, a reaction solution of purified 4- (2-isobutylphenyloxy) trichlorophthalonitrile (10.0 parts by weight), zinc chloride (3.5 parts by weight), and dimethylaminoethanol (300 parts by weight) was heated at 120 ° C. The reaction was performed for 6 hours. The reaction solution was extracted with ethyl acetate and 1N hydrochloric acid, and the organic layer was separated, concentrated, and purified by silica gel chromatography to obtain 8.2 parts by weight of Exemplified Compound A-11.
The maximum absorption wavelength of the obtained compound in chloroform was 705 nm, and the molar extinction coefficient was 145000.

<Exemplary Compound A-24>
Synthesis was performed using 3-isobutylphenol instead of 2-isobutylphenol in the same manner as for Exemplified Compound A-11.
The maximum absorption wavelength of the obtained compound in chloroform was 708 nm, and the molar extinction coefficient was 140000.

<Exemplary Compound A-12)
Dibromourea (44.0 parts by weight) was mixed with a solution of 4-hydroxyphthalonitrile (42.0 parts by weight) and sulfuric acid (300 parts by weight), and reacted at room temperature for 3 hours. The reaction solution was extracted with ethyl acetate and water, and the organic layer was separated, concentrated, and purified by silica gel chromatography. 3-Bromo-4-hydroxyphthalonitrile (14 parts by weight) and 3,5-dibromo-4-hydroxyphthalonitrile (10 parts by weight) were obtained.
A mixture of 3-bromo-4-hydroxyphthalonitrile (14 parts by weight), dodecyl bromide (18 parts by weight), potassium carbonate (20 parts by weight), and N-methylpyrrolidone (200 parts by weight) was obtained. The reaction was carried out at 6 ° C for 6 hours. The reaction solution was extracted with ethyl acetate and 1N hydrochloric acid, and the organic layer was separated, concentrated, and purified by silica gel chromatography to obtain 3-bromo-4-dodecyloxyphthalonitrile (15.0 parts by weight). .
The obtained 3-bromo-4-dodecyloxyphthalonitrile (10 parts by weight) was cyclized in the same manner as Example Compound A-7 to obtain 5 parts by weight of Example Compound A-12.
The maximum absorption wavelength of the obtained compound in chloroform was 698 nm, and the molar extinction coefficient was 130,000.

<Exemplary Compound A-13>
Cyclization was performed using 3,5-dibromo-4-hydroxyphthalonitrile (10.0 parts by weight) in the same manner as Example Compound A-7, to obtain 5 parts by weight of Example Compound A-12.
The maximum absorption wavelength of the obtained compound in chloroform was 700 nm, and the molar extinction coefficient was 135,000.

<Exemplary Compound A-14>
In the same manner as for Exemplified Compound A-12, using dichlorohydantoin instead of dibromourea, 3-chloro-4-hydroxyphthalonitrile (10 parts by weight), 3,5-chloro-4-hydroxyphthalonitrile ( 7 parts by weight) were obtained.
By cyclization using 3-chloro-4-hydroxyphthalonitrile (10 parts by weight) in the same manner as in Example Compound A-7, 7 parts by weight of Example Compound A-14 was obtained.
The maximum absorption wavelength of the obtained compound in chloroform was 682 nm, and the molar extinction coefficient was 115000.
<Exemplary Compound A-15>
By cyclization using 3,5-dichloro-4-hydroxyphthalonitrile (7 parts by weight) in the same manner as for Example Compound A-7, 3 parts by weight of Example Compound A-15 was obtained.
The maximum absorption wavelength of the obtained compound in chloroform was 691 nm, and the molar extinction coefficient was 125000.

<Synthesis of Exemplified Compounds A-16 to A-23>
Zinc phthalocyanine represented by Exemplified Compounds A-16 to A-23 uses zinc chloride in place of copper acetate, using the same intermediate as the synthesis of copper phthalocyanine represented by Exemplified Compounds A-7 to A-15. Was synthesized.

Example 1
For the phthalocyanine compound, the maximum absorption wavelength (λmax) in a chloroform solvent was measured using an ultraviolet-visible spectrophotometer (UV2400-PC manufactured by Shimadzu Corporation). The measurement results are shown in the following table.

（Ｔ－１）光重合性化合物：カヤラドＤＰＨＡ（日本化薬（株）製、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートとの混合物）
（Ｕ－１）バインダー樹脂：ベンジルメタクリレート／メタクリル酸（８５／１５［質量比］共重合体（重量平均分子量：１２，０００）のプロピレングリコールモノメチルエーテルアセテート溶液（固形分４０．０質量％）酸価（１００ｍｇＫＯＨ／ｇ）
（Ｖ－１）光重合開始剤：２－（ベンゾイルオキシイミノ）－１－［４－（フェニルチオ）フェニル］－１－オクタノン（チバスペシャルティケミカルズ社製）
（Ｖ－２）光重合開始剤：２－（アセトキシイミノ）－４－（４－クロロフェニルチオ）－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－ブタノン（チバスペシャルティケミカルズ社製）
（Ｖ－３）光重合開始剤：下記構造のオキシム系化合物

（Ｖ－４）光重合開始剤：イルガキュア３６９（チバスペシャルティケミカルズ社性：αアシルアミノ系化合物）
（Ｖ－５）２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール（Ｂ-ＣＩＭ　保土ヶ谷化学工業製）
（Ｗ－１）光重合開始助剤：４，４’－ビス（ジエチルアミノ）ベンゾフェノン（チバスペシャルティケミカルズ社製）
（Ｗ－２）２－メルカプトベンゾチアゾール（東京化成社製）
（Ｘ－１）溶剤：プロピレングリコールモノメチルエーテルアセテート
（Ｘ－２）溶剤：３－エトキシプロピオン酸エチル
（Ｚ－１）界面活性剤：メガファックＦ７８１－Ｆ（大日本インキ化学工業（株）製）
（Ａ－１０１）特許第３４７６２０８号記載の方法で合成したＣ．Ｉ．アシッドブルー２４９のドデシルアミド化物
（Ａ－１０２）国際公開ＷＯ２０１１／１０５６０３号パンフレットの段落番号０２２６に記載の化合物 Next, each component used for preparation of a colored curable composition is shown below. (Y-1) C.I. I. Pigment Yellow 150 (12.8 parts) and methyl methacrylate / methacrylic acid (80/20) [mass ratio] copolymer (weight average molecular weight: 12,000) (7.2 parts) are mixed with propylene glycol monomethyl ether acetate (80.0). And a pigment dispersion (Y-2) C. obtained by sufficiently dispersing the pigment using a bead mill. I. Solvent Yellow 162) in which 10.0 parts of propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in 90.0 parts (Y-3) 10.0 parts by weight of the following yellow dye is tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) Made in 90.0 parts

(T-1) Photopolymerizable compound: Kayalad DPHA (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
(U-1) Binder resin: benzyl methacrylate / methacrylic acid (85/15 [mass ratio] copolymer (weight average molecular weight: 12,000) in propylene glycol monomethyl ether acetate solution (solid content: 40.0 mass%) Value (100mgKOH / g)
(V-1) Photopolymerization initiator: 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone (manufactured by Ciba Specialty Chemicals)
(V-2) Photopolymerization initiator: 2- (acetoxyimino) -4- (4-chlorophenylthio) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1-butanone (Ciba Specialty Chemicals)
(V-3) Photopolymerization initiator: an oxime compound having the following structure

(V-4) Photopolymerization initiator: Irgacure 369 (Ciba Specialty Chemicals Inc .: α-acylamino compound)
(V-5) 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (B-CIM manufactured by Hodogaya Chemical Co., Ltd.)
(W-1) Photopolymerization initiation assistant: 4,4′-bis (diethylamino) benzophenone (manufactured by Ciba Specialty Chemicals)
(W-2) 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
(X-1) Solvent: Propylene glycol monomethyl ether acetate (X-2) Solvent: Ethyl 3-ethoxypropionate (Z-1) Surfactant: Megafac F781-F (manufactured by Dainippon Ink & Chemicals, Inc.)
(A-101) C.I. synthesized by the method described in Japanese Patent No. 3476208. I. Acid Blue 249 dodecyl amidated compound (A-102) Compound described in paragraph No. 0226 of International Publication WO2011 / 105603 Pamphlet

<Preparation of colored film>
Preparation of colored curable composition (coating liquid) Components in the following composition were mixed to prepare a colored curable composition 1.
<Composition>
・ Exemplary Compound A-1 ... 6.9 parts by mass-(T-1) ... 103.4 parts by mass-(U-1) ... 212.2 parts by mass (in terms of solid content) (Value: 84.9 parts by mass)
· (V-1) · · · 21.2 parts by mass · (W-1) · · · 3.5 parts by mass · · (X-1) · · · 71.9 parts by mass · (X-2) ... 3.6 parts by mass, (Z-1) ... 0.06 parts by mass

(Preparation of colored film by curable colored curable composition)
The colored curable composition (color resist solution) obtained above is placed on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning) so that the maximum absorbance at 600 to 700 nm is 1.5 to 2.0. And dried in an oven at 100 ° C. for 180 seconds to produce a colored film on the substrate.

(Evaluation of colored film by curable colored curable composition)
The following evaluation was performed about the board | substrate obtained above.
<Evaluation of hue>
About the produced colored film, the absorption in 550 nm and 650 nm was measured with the ultraviolet visible spectrophotometer (Shimadzu Corporation UV2400-PC). Based on the obtained results, the transmittance ratio (550 nm / 650 nm) was calculated and evaluated as follows.
○: Less than 0.1 Δ: 0.1 or more and less than 1.0 ×: 1.0 or more

　上記フタロシアニン化合物は、上述の例示化合物の番号に対応している。
　上記結果から明らかなとおり、本発明の着色硬化性組成物を用いることにより、透過部と非透過部のコントラストに優れたカラーフィルタを作製できることが確かめられた。 Other Examples and Comparative Examples In the above, the same procedure was followed except that the phthalocyanine compound was replaced with the following phthalocyanine compound. The results are shown in the table below.

The said phthalocyanine compound respond | corresponds to the number of the above-mentioned exemplary compound.
As is clear from the above results, it was confirmed that a color filter excellent in contrast between the transmissive part and the non-transmissive part can be produced by using the colored curable composition of the present invention.

Example 101
Preparation of green colored film (Preparation of colored curable composition (coating solution))
Components in the following composition were mixed to prepare a colored curable composition.
<Composition>
Exemplified Compound A-1 ... 6 parts by mass Yellow colored substance ((Y-2)) ... Absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05 The amount of yellow coloring was adjusted and added to fit.
-(T-1) ... 103.4 parts by mass-(U-1) ... 212.2 parts by mass (solid content conversion value: 84.9 parts by mass)
· (V-1) · · · 21.2 parts by mass · (W-1) · · · 3.5 parts by mass · · (X-1) · · · 71.9 parts by mass · (X-2) ... 3.6 parts by mass, (Z-1) ... 0.06 parts by mass

The obtained composition was evaluated in the same manner as in Example 1 above. The results are shown in the table below.

Examples 102 to 106, Comparative Example 102
In Example 101, the phthalocyanine compound and the yellow colored product were changed as described in the following table, and the others were performed in the same manner. The results are shown in the table below.

<Light resistance>
The colored film was irradiated with a xenon lamp at 200,000 lux for 10 hours (equivalent to 2 million lux · h), and then the chromaticity change, that is, ΔEab value was measured. A smaller ΔEab value indicates better light resistance.

<Heat resistance>
After the colored film was heated at 230 ° C. for 60 minutes, the chromaticity change, that is, ΔEab value was measured. A smaller ΔEab value indicates better light resistance.

<Residue>
A colored film was prepared in the same manner as in Example 1, then immersed in a sodium bicarbonate / sodium carbonate aqueous solution adjusted to 23 ° C. and pH 12.0 as a developer for 60 seconds, and then washed with ion-exchanged water at 23 ° C. Then, a substrate for residue evaluation was prepared.
The developed substrate was measured with an ultraviolet-visible spectrophotometer (UV2400-PC, manufactured by Shimadzu Corp.), and the residue was evaluated by the maximum absorbance at 400 nm to 700 nm as follows.
○: Maximum absorbance less than 0.05 ×: Maximum absorbance 0.05 or more

As is clear from the above results, it was confirmed that by using the colored curable composition of the present invention, a green filter excellent in contrast between the transmission part and the non-transmission part can be produced.

Claims (15)

It is soluble in an organic solvent, and the main absorption in a chloroform solvent is in the range of 680 nm to 800 nm. At least one of a chlorine atom and a bromine atom and a substitution represented by the following general formula (1) A colored curable composition containing a phthalocyanine compound having a partial structure having one or more of the above.

(In general formula (1), X ¹ represents an oxygen atom, sulfur atom, SO ₂ group or NH group, and R ¹ represents an alkyl group or an aryl group.) The colored curable composition according to claim 1, wherein the phthalocyanine compound is represented by the following general formula (2).

(In the general formula (2), M represents Cu, Zn, V (═O), Mg, Ni, Ti (═O), Mg, Sn, or Si. At least one of A, B, C, and D represents And has a structure represented by the following general formula (3), and the others represent aromatic rings.)

(Xa in the general formula (3) represents a chlorine atom or a bromine atom, at least one of R ² , R ³ and R ⁴ represents a group of the general formula (1), and the rest is a hydrogen atom or a chlorine atom A bromine atom.) The colored curable composition according to claim 1 or 2, wherein M is Cu, Zn or V (= O). The colored curable composition according to claim 2 or 3, wherein A, B, C and D in the general formula (1) are each represented by the general formula (3). The colored curable composition according to claim 2 or 3, wherein A, B, C and D in the general formula (1) are represented by the same general formula (3). The colored curing according to claim 2 or 3, wherein one of R ² and R ³ represents a group of the general formula (1), and the remainder of R ² , R ³ and R ⁴ is a hydrogen atom, a chlorine atom or a bromine atom. Sex composition. The colored curable composition according to any one of claims 1 to 6, further comprising a polymerizable compound and a photopolymerization initiator. The colored curable composition according to claim 7, wherein the photopolymerization initiator is an oxime compound or a biimidazole compound. The colored curable composition according to any one of claims 1 to 8, further comprising a yellow colorant. The colored curable composition according to claim 9, wherein the yellow colorant is an azo dye or a monomethine dye. The colored curable composition according to claim 10, wherein the yellow colorant is a monomethine dye represented by the following general formula (4).

(In general formula (4), R ¹¹ represents an alkyl group, and R ¹² represents an aromatic ring group having a substituent.) A color filter having a colored layer using the colored curable composition according to any one of claims 1 to 11. A step of applying the colored curable composition according to any one of claims 1 to 11 on a substrate to form a colored layer, exposing the formed colored layer in a pattern, developing and coloring Forming a region, and a method of manufacturing a color filter. A liquid crystal display device or a solid-state imaging device having the color filter according to claim 12 or the color filter produced by the method for producing a color filter according to claim 13. Any one of the following compounds A-1 to A-24.