JP2012168258A - Colored curable composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable composition which provides a good skirt-like part in a short wavelength absorption region and has heat resistance.SOLUTION: A colored curable composition comprises (A) a cyanine dye or a squarylium dye which shows an absorption maximum of 720 nm or more in methanol, (B) an alkali-soluble polymer which has a carboxylic acid, sulfonic acid or phosphoric acid value of 150 mgKOH/g or less, and (C) a polymerizable compound. The dye(A) has the absorption maximum of 620 to 670 nm in the alkali-soluble polymer(B).

Description

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

  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 required. 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 the pigment and the increase in viscosity due to poor dispersion stability are likely 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, triarylmethane dyes such as dipyrromethene dyes, pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes, and compounds having a wide variety of dye bases are known (for example, see Patent Documents 2 to 5).

JP-A-6-75375 JP 2008-292970 A JP 2007-039478 A Japanese Patent Laid-Open No. 06-230210 JP 2010-256598 A

  However, these dyes have a problem in that the color purity is lowered and the luminance is lowered due to poor short-wave absorption on the short wave absorption side. Further, when producing a green color filter, it is difficult to form a green filter in combination with a yellow colorant because the above-described dye is too short. Further, when used as a color filter, heat resistance is required.

  The present invention has been made in view of the above, and an object of the present invention is to provide a colored curable composition having excellent heat resistance on the short wave absorption side and having heat resistance. Furthermore, it aims at providing the colored curable composition which can form the filter for green which was excellent in combination with the yellow colorant.

  Under such circumstances, as a result of intensive studies by the inventor of the present application, a cyanine dye or squarylium dye having an absorption maximum at a specific wavelength and containing a hydrophobic counter salt is added to the hydrophobic polymer. It has been found that the absorption maximum can be shifted to the short wave side and that the pulling is excellent, and the present invention has been completed.

（式中、Ｒ₁〜Ｒ₅₀は、それぞれ、水素、アルキル基、アルコキシ基、ヒドロキシル基、エーテル基、チオール基、アリールアミノ基、アルキルアミノ基、チオエーテル基、アルコキシカルボニル基、カルバモイル基、スルファモイル基、アリールケト基、アルキルケト基、シアノ基、ハロゲン原子、アリール基またはヘテロアリール基である。Ｒ₁〜Ｒ₅₀は、それぞれ、縮環可能な部位間において脂肪族性、芳香族性の環を形成しても良く、置換基を有していても良い。
ｎは１〜３の整数である。
Ｘは、酸素原子、硫黄原子又はＣＲ₅₁Ｒ₅₂で示され、Ｒ₅₁、Ｒ₅₂は、それぞれ、アルキル基である。
Ｍ^-は、シアニン染料の対アニオンであり、ＢＦ^4-、ＰＦ^6-、ＳｂＦ^6-または、下記記一般式（Ｖ）で表されるアニオンである：

（式中、Ｒ₅₃、Ｒ₅₄は、それぞれ、パーフルオロアルキル基またはパーフルオロアリール基である。）

（式中、Ｒ₅₅〜Ｒ₇₂は、それぞれ、水素、アルキル基、アルコキシ基、ヒドロキシル基、エーテル基、チオール基、アリールアミノ基、アルキルアミノ基、チオエーテル基、アルコキシカルボニル基、カルバモイル基、スルファモイル基、アリールケト基、アルキルケト基、シアノ基、ハロゲン、アリール基、又はヘテロアリール基である。Ｒ₅₅〜Ｒ₇₂は、それぞれ、縮環可能な部位間において脂肪族性、芳香族性の環を形成しても良く、置換基を有していても良い。Ｘは、酸素原子、硫黄原子又はＣＲ₅₁Ｒ₅₂で示され、Ｒ₅₁、Ｒ₅₂は、それぞれ、アルキル基である。）
（５）さらに、前記（Ａ）染料と異なる着色化合物（Ｄ）を含む、（１）〜（４）のいずれか１項に記載の着色硬化性組成物。
（６）着色化合物（Ｄ）が黄色着色化合物である、（５）に記載の着色硬化性組成物。
（７）（Ａ）メタノール中における吸収極大が７２０ｎｍ以上を示すシアニン染料、又はスクアリリウム染料、（Ｂ）１５０ｍｇＫＯＨ／ｇ以下のカルボン酸、スルホン酸又はリン酸価を有するアルカリ可溶性ポリマーおよび（Ｃ）重合性化合物を有し、前記（Ａ）染料が、前記（Ｂ）アルカリ可溶性ポリマー中にて、Ｈ会合を形成することを特徴とする着色硬化性組成物。
（８）（１）〜（７）のいずれか１項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。
（９）（１）〜（７）のいずれか１項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。
（１０）（８）に記載のカラーフィルタ、又は（９）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。
（１１）（８）に記載のカラーフィルタ、又は（９）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固体撮像素子。
（１２）下記一般式（ＶＩＩＩ）または（ＩＸ）で表される化合物。

（式中、Ｒ⁸²〜Ｒ⁸⁵は、それぞれ、アルキル基、アルコキシカルボニル基、シアノ基、アリール基、ヘテロアリール基であり、これらの基は置換基を有していても良い。また、Ｒ⁸²〜Ｒ⁸⁵の２つが結合して環を形成していてもよい。
Ｍ^-は、シアニン染料の対アニオンであり、ＢＦ^4-、ＰＦ^6-、ＳｂＦ^6-または、下記記一般式（Ｖ）で表されるアニオンである：

（式中、Ｒ₅₃、Ｒ₅₄は、それぞれ、パーフルオロアルキル基またはパーフルオロアリール基である。）
（１３）（１２）に記載の化合物であって、Ｒ₈₄、Ｒ₈₈、Ｒ₈₅およびＲ₉₆が、それぞれ、アルキル基、アルコキシカルボニル基、シアノ基、アリール基またはヘテロアリール基である化合物、Ｒ₇₃およびＲ₇₅が互いに結合して肪族環または芳香族環を形成している化合物。
（１４）下記化合物。

Specifically, the above problem has been achieved by the following means.
(1) (A) a cyanine dye or squarylium dye having an absorption maximum in methanol of 720 nm or more, (B) an alkali-soluble polymer having a carboxylic acid, sulfonic acid or phosphoric acid value of 150 mgKOH / g or less, and (C) polymerization A colored curable composition comprising an organic compound, wherein the (A) dye has an absorption maximum at 620 to 670 nm in the alkali-soluble polymer (B).
(2) The transmittance ratio (550 nm / 580 nm) of the transmittance at 550 nm and the transmittance at / 580 nm in the (B) alkali-soluble polymer of the (A) dye is 1.2 to 1.0. The colored curable composition as described in (1).
(3) The colored curable composition according to (1) or (2), further comprising a photopolymerization initiator.
(4) The dye (A) is a compound represented by any one of the following general formulas (I), (II), (III), (IV), (VI) and (VII): The colored curable composition of any one of-(3).

(In the formula, R _{1 to} R ₅₀ are respectively hydrogen, alkyl group, alkoxy group, hydroxyl group, ether group, thiol group, arylamino group, alkylamino group, thioether group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group. An arylketo group, an alkylketo group, a cyano group, a halogen atom, an aryl group or a heteroaryl group, wherein R _{1 to} R ₅₀ each form an aliphatic or aromatic ring between the condensable sites. Or may have a substituent.
n is an integer of 1 to 3.
X is an oxygen atom, a sulfur atom or CR ₅₁ R ₅₂ , and R ₅₁ and R ₅₂ are each an alkyl group.
M ⁻ is a counter anion of the cyanine dye, and is BF ⁴⁻ , PF ⁶⁻ , SbF ^6−, or an anion represented by the following general formula (V):

(In the formula, R ₅₃ and R ₅₄ are each a perfluoroalkyl group or a perfluoroaryl group.)

(Wherein R _{55 to} R ₇₂ are each hydrogen, alkyl group, alkoxy group, hydroxyl group, ether group, thiol group, arylamino group, alkylamino group, thioether group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group. An arylketo group, an alkylketo group, a cyano group, a halogen, an aryl group, or a heteroaryl group, each of R _{55 to} R ₇₂ forms an aliphatic or aromatic ring between the condensable sites; X may be an oxygen atom, a sulfur atom, or CR ₅₁ R ₅₂ , and R ₅₁ and R ₅₂ are each an alkyl group.
(5) The colored curable composition according to any one of (1) to (4), further comprising a colored compound (D) different from the (A) dye.
(6) The colored curable composition according to (5), wherein the colored compound (D) is a yellow colored compound.
(7) (A) a cyanine dye or squarylium dye having an absorption maximum in methanol of 720 nm or more, (B) an alkali-soluble polymer having a carboxylic acid, sulfonic acid or phosphoric acid value of 150 mgKOH / g or less, and (C) polymerization A colored curable composition comprising an ionic compound, wherein the (A) dye forms an H association in the (B) alkali-soluble polymer.
(8) A color filter having a colored layer using the colored curable composition according to any one of (1) to (7).
(9) Applying the colored curable composition according to any one of (1) to (7) on a substrate to form a colored layer, and exposing the formed colored layer in a pattern. And a step of developing to form a colored region.
(10) A liquid crystal display device having the color filter according to (8) or the color filter produced by the method for producing a color filter according to (9).
(11) A solid-state imaging device having a color filter according to (8) or a color filter produced by the method for producing a color filter according to (9).
(12) A compound represented by the following general formula (VIII) or (IX).

(Wherein, R ⁸² to R ⁸⁵ are each an alkyl group, an alkoxycarbonyl group, a cyano group, an aryl group, a heteroaryl group, these groups may have a substituent. Further, R ⁸² two members to the to R ⁸⁵ may form a ring.
M ⁻ is a counter anion of the cyanine dye, and is BF ⁴⁻ , PF ⁶⁻ , SbF ^6−, or an anion represented by the following general formula (V):

(In the formula, R ₅₃ and R ₅₄ are each a perfluoroalkyl group or a perfluoroaryl group.)
(13) The compound according to (12), wherein R ₈₄ , R ₈₈ , R ₈₅ and R ₉₆ are each an alkyl group, an alkoxycarbonyl group, a cyano group, an aryl group or a heteroaryl group, R A compound in which ₇₃ and R ₇₅ are bonded to each other to form an aliphatic ring or an aromatic ring.
(14) The following compound.

  According to the present invention, it is possible to provide a colored curable composition having excellent heat resistance on the short wave absorption side and having heat resistance. Furthermore, it has become possible to provide a colored curable composition capable of forming an excellent green filter in combination with a yellow colorant.

  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.

The colored curable composition of the present invention comprises (A) a cyanine dye or squarylium dye having an absorption maximum in methanol of 720 nm or more, and (B) an alkali having a carboxylic acid, sulfonic acid or phosphoric acid value of 150 mgKOH / g or less. It has a soluble polymer and (C) a polymerizable compound, and the (A) dye has an absorption maximum at least at 620 to 670 nm in the (B) alkali-soluble polymer. Preferably, the transmittance ratio of the transmittance at 550 nm and the transmittance at / 580 nm (550 nm / 580 nm) in the (B) alkali-soluble polymer of the (A) dye is 1.2 to 1.0. It is characterized by that.
By adopting such a colored curable composition, a composition excellent in heat resistance and excellent in pulling on the short wave absorption side can be obtained. Here, being excellent in the pulling on the short wave absorption side means having a spectrum showing a steep rise. In particular, in the present invention, the smaller the transmittance ratio at 550 nm / 580 nm, the better the cut at the short wavelength side of the dye. Thus, when it is excellent in the pulling of the short wavelength side, a colored curable composition having high color purity, high brightness and high contrast can be obtained. In particular, in combination with a yellow colorant, a colored curable composition excellent in a color filter for green can be obtained.
In the composition of the present invention, it is considered that the (A) dye forms H association in the (B) alkali-soluble polymer, and as a result, causes the above phenomenon. Although the factor that the cyanine dye and squarylium dye form H aggregates is not clear, it is thought to be caused by the compatibility of the dye molecule and the binder. Formation of H-aggregates of cyanine dye and squarylium dye can be achieved by selecting a binder having hydrophilicity / hydrophobicity derived from an appropriate acid value. The obtained H aggregate has an absorption maximum in the alkaline polymer (B), preferably in the wavelength range of 620 to 670 nm, and more preferably in the range of 630 to 660 nm.
The transmittance ratio (550 nm / 580 nm) of the transmittance at 550 nm and the transmittance at / 580 nm in the (B) alkali-soluble polymer of the (A) dye is preferably 1.2 to 1.0, More preferably, it is 1.1-1.0.
Further, the transmittance of the dye (A) at 550 nm in the alkali-soluble polymer (B) can be 97.0% or more, and more preferably 98.0% or more. The transmittance at 580 nm of the (A) dye in the (B) alkali-soluble polymer can be 85.0% or more, and further can be 90.0% or more.

(A) Cyanine dye or squarylium dye having an absorption maximum in methanol of 720 nm or more The colored curable composition of the present invention contains a cyanine dye or squarylium dye having an absorption maximum in methanol of 720 nm or more. From the viewpoint of hue, the cyanine or squarylium dye useful in the present invention preferably has an absorption maximum position in methanol of 725 nm to 780 nm, and more preferably 730 nm to 770 nm.

  The cyanine dye and squarylium dye used in the present invention are preferably represented by any one of the general formulas (I), (II), (III), (IV), (VI) and (VII).

（式中、Ｒ₁〜Ｒ₅₀は、それぞれ、水素、アルキル基、アルコキシ基、ヒドロキシル基、エーテル基、チオール基、アリールアミノ基、アルキルアミノ基、チオエーテル基、アルコキシカルボニル基、カルバモイル基、スルファモイル基、アリールケト基、アルキルケト基、シアノ基、ハロゲン原子、アリール基またはヘテロアリール基である。Ｒ₁〜Ｒ₅₀は、それぞれ、縮環可能な部位間において脂肪族性、芳香族性の環を形成しても良く、置換基を有していても良い。
ｎは１〜３の整数である。
Ｘは、酸素原子、硫黄原子又はＣＲ₅₁Ｒ₅₂で示され、Ｒ₅₁、Ｒ₅₂は、それぞれ、アルキル基である。
Ｍ^-は、シアニン染料の対アニオンであり、ＢＦ^4-、ＰＦ^6-、ＳｂＦ^6-または、下記記一般式（Ｖ）で表されるアニオンである：

（式中、Ｒ₅₃、Ｒ₅₄は、それぞれ、パーフルオロアルキル基またはパーフルオロアリール基である。） Cyanine dyes (general formulas (I), (II), (III), (IV))

(In the formula, R _{1 to} R ₅₀ are respectively hydrogen, alkyl group, alkoxy group, hydroxyl group, ether group, thiol group, arylamino group, alkylamino group, thioether group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group. An arylketo group, an alkylketo group, a cyano group, a halogen atom, an aryl group or a heteroaryl group, wherein R _{1 to} R ₅₀ each form an aliphatic or aromatic ring between the condensable sites. Or may have a substituent.
n is an integer of 1 to 3.
X is an oxygen atom, a sulfur atom or CR ₅₁ R ₅₂ , and R ₅₁ and R ₅₂ are each an alkyl group.
M ⁻ is a counter anion of the cyanine dye, and is BF ⁴⁻ , PF ⁶⁻ , SbF ^6−, or an anion represented by the following general formula (V):

(In the formula, R ₅₃ and R ₅₄ are each a perfluoroalkyl group or a perfluoroaryl group.)

R ₁ and R ₂ are each preferably a substituted or unsubstituted alkyl group. As for carbon number of an alkyl group, 2-10 are preferable. When it has a substituent, it is preferable that carbon number including carbon number of a substituent is 2-10. The alkyl group may be linear, branched or cyclic, but is preferably linear. As the substituent, a phenyl group, an ether group, and a sulfamoyl group are preferable. These substituents may be further substituted with an alkyl group. In this case, the alkyl group preferably has 1 to 5 carbon atoms. R ₁ and R ₂ are more preferably the same group.

R ₃ , R ₄ and R ₅ are preferably hydrogen atoms.
R ₆ and R ₁₀ are each preferably an alkyl group, an alkoxycarbonyl group, an alkyl group, a phenyl group, or a cyano group. As for carbon number of an alkyl group, 2-10 are preferable. When it has a substituent, it is preferable that carbon number including carbon number of a substituent is 2-10, However, It is preferable that it is an unsubstituted alkyl group. The alkyl group may be linear, branched or cyclic, but is preferably linear. As for carbon number of the alkoxy group of an alkoxycarbonyl group, 1-4 are preferable. R ₆ and R ₁₀ are more preferably the same group.

R ₈ and R ₉ , and R ₁₂ and R ₁₃ are preferably bonded to each other to form a benzene ring. The benzene ring may have a substituent, but is preferably unsubstituted.

R ₇ and R ₁₁ are each preferably a substituted or unsubstituted phenyl group or cyano group. The substituent that the phenyl group may have is preferably an alkyl group having 1 to 4 carbon atoms. R ₇ and R ₁₁ are more preferably the same group.
In general formula (I), n is preferably 1.

R ₃₁ and R ₃₄ are each preferably a substituted or unsubstituted alkyl group. As for carbon number of an alkyl group, 1-10 are preferable. When it has a substituent, it is preferable that carbon number which does not include the carbon number of a substituent is 1-10. As the substituent, a phenyl group is preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear. R ₃₁ and R ₃₄ are more preferably the same group.

R ₃₂ and R ₃₅ are each preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkyl group or a cyano group, and a substituted or unsubstituted phenylene group or substituted Alternatively, an unsubstituted pyridyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a cyano group is more preferable, and a phenylene group, a branched alkyl group, a pyridyl group, or a cyano group is further preferable. R ₃₂ and R ₃₅ are preferably the same group.

R ₂₇ and R ₂₉ are each preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. R ₂₇ and R ₂₉ are preferably the same group.
R ₂₈ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or two R ₂₈ alkyl groups bonded together to form a ring, and a hydrogen atom or two R ₂₈ alkyl groups bonded together. More preferably, a 5-membered ring or a 6-membered ring is formed.
R ₂₅ and R ₃₀ , and R ₂₆ and R ₃₃ are preferably bonded to each other to form a ring, more preferably a benzene ring or a naphthalene ring. These rings may have a substituent, and the substituent is preferably an alkyl group having 1 to 4 carbon atoms. R ₂₅ and R ₃₀ , and R ₂₆ and R ₃₃ are more preferably bonded to each other to form the same ring.
In the general formula (II), n is preferably 2.

R ₂₂ and R ₂₄ are each preferably a substituted or unsubstituted alkyl group. As for carbon number of an alkyl group, 1-10 are preferable. When it has a substituent, it is preferable that carbon number including carbon number of a substituent is 1-10. As the substituent, a phenyl group is preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear. R ₂₂ and R ₂₄ are more preferably the same group.

R ₁₆ , R ₁₈ and R ₂₀ are each preferably a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms. R ₁₆ , R ₁₈ and R ₂₀ are preferably the same group.
R ₁₇ and R ₁₉ are each preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or R ₁₇ and R ₁₉ are combined to form a ring, and a hydrogen atom or R ₁₇ and R ₁₉ are combined. More preferably, a 5-membered ring or a 6-membered ring is formed.
R ₂₁ and R ₁₄ , and R ₁₅ and R ₂₃ are preferably bonded to each other to form a ring, more preferably a benzene ring or a naphthalene ring. These rings may have a substituent, and the substituent is preferably an alkyl group having 1 to 4 carbon atoms. R ₂₁ and R ₁₄ , and R ₁₅ and R ₂₃ are more preferably bonded to each other to form the same ring.
In the general formula (III), n is preferably 1.

R _36, R _37, R ₃₈ and R ₃₉ are each preferably an alkyl group having 1 to 5 carbon atoms, the alkyl group may have a substituent, R ₃₆ and R _37, R ₃₈ and R ₃₉ , R ₃₆ and R ₄₅ , R ₃₇ and R ₄₃ , R ₃₈ and R _48, or R ₃₉ and R ₄₉ may be bonded to each other to form a 5-membered ring or a 6-membered ring. These groups may have a substituent. More preferably, R ₃₆ and R ₃₉ , and R ₃₇ and R ₃₈ are each the same group.
R ₄₃ and R ₄₈ are each preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. As described above, R ₃₇ and R ₄₃ or R ₃₈ and R ₄₈ may be bonded to each other to form a 5-membered ring or a 6-membered ring. R ₄₃ and R ₄₈ are more preferably the same group.
R ₄₅ and R ₄₉ are each a hydrogen atom, an alkyl group or, if bonded to form a 5- or 6-membered ring together with R ₃₆ and R ₄₅ or R ₃₉ and R _49,, R ₄₅ and R It is preferable that ₄₆ or R ₄₉ and R ₅₀ are bonded to each other to form a benzene ring or a 5-membered or 6-membered heterocycle. More preferably, R ₄₅ and R ₄₉ are each a hydrogen atom, an alkyl group, or R ₄₅ and R ₄₆ or R ₄₉ and R ₅₀ which are bonded to each other to form a benzene ring. R ₄₅ and R ₄₉ are more preferably the same group.

R ₄₆ and R ₅₀ are each an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or R ₄₅ and R ₄₆ or R ₄₉ and R ₅₀ to form a benzene ring. It is preferable. R ₄₆ and R ₅₀ are preferably the same group.
R ₄₀ , R ₄₁ and R ₄₂ are preferably hydrogen atoms.
In general formula (IV), n is preferably 1.
M ⁻ is preferably bis (trifluoromethanesulfonyl) imide lithium, BF ⁴⁻ , PF ^6−, or SbF ⁶⁻ .

（式中、Ｒ⁸²〜Ｒ⁸⁵は、それぞれ、アルキル基、アルコキシカルボニル基、アリール、シアノ基、アリール基、ヘテロアリール基であり、これらの基は置換基を有していても良い。また、Ｒ⁸²〜Ｒ⁸⁵の２つが結合して環を形成していてもよい。
Ｍ^-は、シアニン染料の対アニオンであり、ＢＦ^4-、ＰＦ^6-、ＳｂＦ^6-または、下記記一般式（Ｖ）で表されるアニオンである：

（式中、Ｒ₅₃、Ｒ₅₄は、それぞれ、パーフルオロアルキル基またはパーフルオロアリール基である。） The cyanine dye is more preferably a compound represented by the following general formula (VIII) or (IX).

(Wherein R ^{82 to} R ⁸⁵ are each an alkyl group, an alkoxycarbonyl group, an aryl, a cyano group, an aryl group, or a heteroaryl group, and these groups may have a substituent. two of R ⁸² to R ⁸⁵ may be combined with each other to form a ring.
M ⁻ is a counter anion of the cyanine dye, and is BF ⁴⁻ , PF ⁶⁻ , SbF ^6−, or an anion represented by the following general formula (V):

(In the formula, R ₅₃ and R ₅₄ are each a perfluoroalkyl group or a perfluoroaryl group.)

In the formula (VIII), R ₈₆ is R ₁ , R ₈₈ is R ₇ , R ₈₄ is R ₆ , R ₈₅ is R ₁₀ , R ₉₆ is R ₁₁ , R ₈₇ is R ₂ , R ₉₃ R ₃ , R ₉₅ is R ₅ , and R ₉₄ is R _4, and the preferred ranges are the same.
R ₈₉ , R ₉₀ , R ₉₁ , R ₉₂ , R ₉₇ , R ₉₈ , R ₉₉ and R ₁₀₀ are each a hydrogen atom, or R ₈₉ , R ₉₂ , R ₉₇ and R ₁₀₀ are each a hydrogen atom. R ₉₀ and R ₉₁ and R ₉₈ and R ₉₉ are preferably bonded to each other to form a 5-membered ring.
In formula (IX), R ₆₇ and R _31, R ₈₂ and R _32, R ₇₂ and R _27, R ₇₄ and R _27, R ₇₆ and R _29, R ₈₃ and R _35, R ₈₁ R ₃₄ , R ₇₃ is R ₂₈ , and R ₇₅ is R _28, and the preferred ranges are the same.
R ₆₈ , R ₆₉ , R ₇₀ , R ₇₁ , R ₇₇ , R ₇₈ , R ₇₉ and R ₈₀ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, or R ₇₀ , R ₇₁ , R _77. And R ₇₈ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₆₈ and R ₆₉ and R ₇₉ and R ₈₀ are preferably bonded to each other to form a benzene ring.

In particular, in the general formula (VI), R ₈₄ , R ₈₈ , R ₈₅ and R ₉₆ are each preferably an alkyl group, an alkoxycarbonyl group, a cyano group, an aryl group or a heteroaryl group, and an alkyl group, an alkoxycarbonyl group, A cyano group or an aryl group is more preferable, and an alkyl group or an aryl group is further preferable.
In particular, in general formula (IX), it is preferable that R ₇₃ and R ₇₅ are bonded to each other to form an aliphatic ring or an aromatic ring.

（式中、Ｒ₅₅〜Ｒ₇₂は、それぞれ、水素、アルキル基、アルコキシ基、ヒドロキシル基、エーテル基、チオール基、アリールアミノ基、アルキルアミノ基、チオエーテル基、アルコキシカルボニル基、カルバモイル基、スルファモイル基、アリールケト基、アルキルケト基、シアノ基、ハロゲン、アリール基、又はヘテロアリール基である。Ｒ₅₅〜Ｒ₇₂は、それぞれ、縮環可能な部位間において脂肪族性、芳香族性の環を形成しても良く、置換基を有していても良い。Ｘは、酸素原子、硫黄原子又はＣＲ₅₁Ｒ₅₂で示され、Ｒ₅₁、Ｒ₅₂は、それぞれ、アルキル基である。） Squarylium dyes (general formulas ((VI) and (VII))

(Wherein R _{55 to} R ₇₂ are each hydrogen, alkyl group, alkoxy group, hydroxyl group, ether group, thiol group, arylamino group, alkylamino group, thioether group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group. An arylketo group, an alkylketo group, a cyano group, a halogen, an aryl group, or a heteroaryl group, each of R _{55 to} R ₇₂ forms an aliphatic or aromatic ring between the condensable sites; X may be an oxygen atom, a sulfur atom, or CR ₅₁ R ₅₂ , and R ₅₁ and R ₅₂ are each an alkyl group.

R ₅₅ , R ₅₆ , R ₅₇ and R ₅₈ are each preferably a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms. R ₆₁ , R ₆₂ , R ₆₃ and R ₆₄ are preferably hydrogen atoms. R ₅₉ and R ₆₀ and R ₆₅ and R ₆₆ are preferably bonded to each other to form a benzene ring.

R ₆₇ and R ₆₈ and R ₆₉ and R ₇₀ are preferably bonded to each other to form a benzene ring or a naphthalene ring. The benzene ring or naphthalene ring may further have a substituent.
R ₇₁ and R ₇₂ are each preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
X is preferably a sulfur atom or CR ₅₁ R ₅₂ , and R ₅₁ and R ₅₂ are preferably a methyl group.

Hereinafter, preferred substituents in the present invention will be described. The alkyl group is preferably a linear, branched, or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and butyl. Group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group) Is mentioned.
The alkoxy group is preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. For example, methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxy group , A dodecyloxy group, a cycloalkyloxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group, and an aryloxy group is preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, A phenoxy group, a 1-naphthoxy group, and preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably a heterocyclic oxy group having 1 to 18 carbon atoms, such as a 1-phenyltetrazole-5-oxy group , 2-tetrahydropyranyloxy group, preferably a silyloxy group having 1 to 3 carbon atoms More preferably a silyloxy group having 1 to 18 carbon atoms, for example, a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, or a diphenylmethylsilyloxy group, and an acyloxy group preferably has 2 to 48 carbon atoms, more preferably Examples of the acyloxy group having 2 to 24 carbon atoms include an acetoxy group, a pivaloyloxy group, a benzoyloxy group, and a dodecanoyloxy group. A plurality of alkoxy groups may form a ring structure via an aliphatic group.

The alkoxycarbonyl group is preferably an alkyl group or cycloalkyl group having 1 to 48 carbon atoms, more preferably 1 to 18 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-butylcarbonyl group, t- A butylcarbonyl group, a cyclohexylcarbonyl group, etc. are mentioned.
The ether group or thioether group is preferably a (thio) ether group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methyl (thio) ether group, an ethyl (thio) ether group, 1-butyl ( A thio) ether group, a 2-butyl (thio) ether group, a t-butyl (thio) ether group, a dodecyl (thio) ether group, a cyclohexyl (thio) ether group, and the like.
The carbamoyl group is preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. For example, a carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N -Dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group.
The sulfamoyl group is preferably a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methanesulfonamide group, butanesulfonamide group, octanesulfonamide group, benzenesulfonamide group, hexadecanesulfone. An amide group, a cyclohexanesulfonamido group) or a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N, N-dipropyls). A rufamoylamino group and an N-ethyl-N-dodecylsulfamoylamino group are preferable structures, and examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The aryl group is preferably an aryl group having 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms, such as a phenyl group, a naphthyl group, or a tolyl group, and the heteroaryl group is preferably 1 to 24 carbon atoms, more preferably Is a 1-12 heteroaryl group, for example, 2-thienyl group, 4-pyridyl group, 2-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl. Group, 1-pyrazolyl group, benzotriazol-1-yl group) and the like.

  Alkyl groups, alkoxy groups, hydroxyl groups, ether groups, thiol groups, arylamino groups, alkylamino groups, thioether groups, alkoxycarbonyl groups, carbamoyl groups, sulfamoyl groups, represented by the general formulas (I) to (VII) When the arylketo group, the alkylketo group, the cyano group, the halogen, the aryl group, or the heteroaryl group is a further substitutable group, it may be substituted with the substituent described above, and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.

  Next, specific examples of the cyanine dye and squarylium dye used in the present invention are shown below. However, the present invention is not limited to these. In the following compounds, Et represents an ethyl group, Ph represents a phenyl group, and Me represents a methyl group.

The compounds of the general formulas (I) to (IV) are described in U.S. Pat. Nos. 2,231,658, 2,233,511, Ch.
emistry of Heterocyclic Compounds (New York, NY, United States), 1988, p.736-740, Angelwandte Chemie, International Edition, 2009, vol.48, # 35 p.6480-6484, the above general formula (VI) or ( The compound of VII) is Chemistry--A European Journal,
2010, vol.16, # 17 p.5129-5137, Chemical Communications (Cambridge, United Kingdom), 2010, vol.46, # 23 p.4073-4075, and the like.

In the colored curable composition of this invention, a cyanine dye and squarylium dye may be contained individually by 1 type, and may be used together 2 or more types.
The content of the cyanine dye and squarylium dye used in the present invention in the colored curable composition varies depending on the molecular weight and its extinction coefficient, but is 1 to 70% by mass based on the total solid content of the colored curable composition. Preferably, 5-50 mass% is more preferable. When the dye content is 5% 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 is good. Is more advantageous.

Alkali-soluble polymer having carboxylic acid, sulfonic acid or phosphoric acid value of 150 mgKOH / g or less The colored curable composition of the present invention comprises an alkali-soluble polymer having a carboxylic acid, sulfonic acid or phosphoric acid value of 150 mgKOH / g or less. . By selecting the polymer acid value (derived from hydrophilicity / hydrophobicity), it is possible to shift the wavelength of the absorption maximum of the cyanine dye and squarylium dye used in the present invention to the short wavelength side, and to further improve the pulling of the short wavelength side. . This is considered to be based on the fact that the cyanine dye or squarylium dye used in the present invention forms H aggregates in the alkali-soluble polymer. The original absorption maximum of cyanine dye and squarylium dye remains, and the absorption maximum there may be larger.
The alkali-soluble polymer having a carboxylic acid, sulfonic acid or phosphoric acid value of 150 mgKOH / g or less in the present invention is particularly limited except that it can form an H-aggregate of a dye due to moderate hydrophobicity derived from a low acid value. Preferably, it can be selected from the viewpoints of heat resistance, developability, availability and the like.
The alkali-soluble polymer has an acid value of 130 mgKOH / g to 50 mgKOH / g, more preferably 120 to 70 mgKOH / g from the viewpoint of developability.

  The alkali-soluble polymer is preferably a linear organic polymer and is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

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

  The alkali-soluble polymer may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the polymer containing the above-described polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble polymers, 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 control of developability. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include copolymers composed of monomers selected from allyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available products. KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.

The alkali-soluble polymer is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ from the viewpoint of developability, liquid viscosity, etc., and a weight of 2000 to 1 × 10 ⁵ A coalescence is more preferable, and a polymer of 5000 to 5 × 10 ⁴ is particularly preferable.

(C) Polymerizable compound The colored curable composition of the present invention 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 the 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, as the itaconic acid ester, for example, 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 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. 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.

Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. 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 functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid esters, methacrylic acid esters, styrene compounds, vinyl ether compounds). It is also effective to adjust both sensitivity and intensity by using together. 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.

  The colored curable composition of the present invention further contains a photopolymerization initiator, a coloring compound, an organic solvent, a crosslinking agent, a surfactant, a filler, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, an increase, if necessary. Various additives such as a sensitizer and a light stabilizer may be contained.

[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 a halomethyl oxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone compound. And derivatives thereof, cyclopentadiene-benzene-iron 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 is preferable from the viewpoint of rapid polymerization reaction.

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

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

（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 is an integer of 1 to 5. .)

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

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

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

X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Group, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have an amino group and an amino group which may have a substituent are preferable.
Moreover, n in General formula (1) has a preferable integer of 1-2.

  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 (total content in the case of two or more) of the colored curable composition of the photopolymerization initiator in the total solid content is 3% by mass to 20% by mass from the viewpoint of obtaining the effect of the present invention more effectively. % Is preferable, 4% by mass to 19% by mass is more preferable, and 5% by mass to 18% by mass is particularly preferable.

[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 2001-10881 A). 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, and the like.

  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 Pigment Yellow 188 Disazo Compound Pigments, 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 colored product is preferably a yellow colored compound, more preferably a pigment yellow 150 or pigment yellow 139 as a pigment, 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 may be mentioned.

When the dye or pigment is blended as a dispersion, it can be adjusted according to the description in JP-A-9-197118 and JP-A-2000-239544.
Content of the said dye or pigment can be used in the range which does not impair the effect of this invention, and is 0.5 mass%-70 mass% with respect to the total solid of the colored curable composition of this 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.

[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 and the like (specifically, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, 3-ethoxy Ethyl propionate, etc.)), 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (specifically, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), 2-oxy-2-methylpropionic acid Methyl, ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate , Methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.

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

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of each of the above-described components, and the solubility of the above-described components and the improvement of the coating surface state when an alkali-soluble polymer is included. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol 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, and more preferably 15% by mass to 60% by mass. .

[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. As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) (Manufactured by Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.) and PolyFox (manufactured by OMNOVA).

  Further, as the surfactant, it contains a repeating unit A and a repeating unit B represented by the following general formula (1), and has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography of 1,000 or more and 10 A copolymer having a molecular weight of 1,000 or less can be cited as a preferred example.

（式（１）中、Ｒ¹及びＲ³はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ²は炭素数１〜４の直鎖アルキレン基を表し、Ｒ⁴は水素原子又は炭素数１〜４のアルキル基を表し、Ｌは炭素数３〜６のアルキレン基を表し、ｐ及びｑは重合比を表す重量百分率であり、ｐは１０重量％〜８０重量％の数値を表し、ｑは２０重量％〜９０重量％の数値を表し、ｒは１〜１８の整数を表し、ｎは１〜１０の整数を表す。）
前記式（１）におけるＬは、下記式（２）で表される分岐アルキレン基であることが好ましい。

(In formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or 1 carbon atom. Represents an alkyl group having ˜4, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, p represents a numerical value of 10 wt% to 80 wt%, and q is (A numerical value of 20% by weight to 90% by weight is represented, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.)
L in the formula (1) is preferably a branched alkylene group represented by the following formula (2).

（式（２）中、Ｒ⁵は、炭素数１〜４のアルキル基を表し、相溶性と被塗布面に対する濡れ性の点で、炭素数１〜３のアルキル基が好ましく、炭素数２または３のアルキル基がより好ましい。

(In Formula (2), R ⁵ represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. More preferred is an alkyl group of 3.

The weight average molecular weight (Mw) of the copolymer represented by the general formula (1) is more preferably 1,500 or more and 5,000 or less.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The amount of (I) surfactant added in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, and 0.01 to 10 parts by weight with respect to 100 parts by weight of the specific resin (A). More preferably, it is more preferably 0.01 to 1 part by weight.

[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 0.01 μm to 3.0 μm, more preferably a pore size of 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 through 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 microliter / second to 2000 microliter / second, preferably 800 microliter / second to 1500 microliter / second. The speed is usually 50 mm / second to 300 mm / second, preferably 100 mm / second to 200 mm / second.
Further, the solid content of the colored curable composition used in the coating step is usually 10% to 20%, preferably 13% to 18%.

When forming the coating film by the colored curable composition of this invention on a board | substrate, as thickness (after a prebaking process) of this coating film, it is generally 0.3 micrometer-5.0 micrometers, Preferably 0.5 micrometer-4 0.0 μm, 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 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
The thickness of the colored curable composition layer formed from the colored curable composition is appropriately selected according to the purpose. In the color filter for liquid crystal display devices, 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 the most preferable. Moreover, in the color filter for solid-state image sensors, the range of 0.2 micrometer-5.0 micrometers is preferable, The range of 0.3 micrometer-2.5 micrometers is more preferable, The range of 0.3 micrometer-1.5 micrometers is the 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 exposure object (pattern), in the range of ^{1mJ / cm 2 ~100mJ / cm 2} , the range of 1mJ / cm ² ~50mJ / cm ² is more preferable. An exposure amount within this range is preferable from the viewpoint of pattern formation productivity.

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. Concentrations of alkaline compounds such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 0.001% by mass to 10% by mass, preferably 0.01 The alkaline aqueous solution melt | dissolved so that it may become 1 mass%-1 mass% is mentioned. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to be 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 of 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.

-Step (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.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. 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 Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a horizontal 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 fine COA (Color-filter On Array) system.

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

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

(Synthesis Example 1: Synthesis of Exemplified Compound (S-4))
1-1. Synthesis of Synthetic Intermediate (S-4A) 2'-aminoacetophenone (8.5 g, manufactured by Tokyo Chemical Industry Co., Ltd.) and benzyl phenyl ketone (11.76 g) (manufactured by Tokyo Chemical Industry Co., Ltd.) were acetic acid (40 ml, manufactured by Wako Pure Chemical Industries, Ltd.). ) Was mixed and dissolved at room temperature (25 ° C.). Next, concentrated sulfuric acid (7.0 g, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was stirred and reacted at 110 ° C. for 10 hours. After cooling the reaction solution, it was reprecipitated in 300 ml of water, and the resulting precipitate was filtered and dried to obtain a synthetic intermediate S-4A crude product.
Further, ethyl acetate (200 ml) was added to the filtrate, neutralized to pH 7 with sodium bicarbonate, the ethyl acetate layer was separated, dried over magnesium sulfate and concentrated to obtain a synthetic intermediate S-4A crude product. . Next, the obtained two S-4A crude bodies were mixed, stirred with acetone (50 ml) at room temperature for 1 hour, and the precipitate was filtered and dried to obtain a synthetic intermediate S-4A (8.9 g). (Yield 50%).

1-2. Synthesis of synthetic intermediate (S-4B) S-4A (0.9 g) and iodobutane (1.12 g, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed with sulfolane (1 ml, manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C.). I let you. Next, the reaction solution was stirred and reacted at 140 ° C. for 4 hours. After cooling the reaction solution, it was reprecipitated in ethyl acetate (10 ml), and the resulting precipitate was filtered and dried to obtain synthetic intermediate S-4B (0.33 g) (yield 23%).

1-3. Synthesis of Illustrative Compound (S-4) Synthetic simplified form (S-4A) (0.33 g) obtained as described above and ethyl orthoformate (0.15 g, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed with pyridine (1 ml, Wako Pure Chemical Industries, Ltd.) was mixed and dissolved at room temperature (25 ° C.). Next, the reaction solution was stirred and reacted at 120 ° C. for 10 hours. After cooling the reaction solution, it was reprecipitated in 300 ml of water, and the resulting precipitate was filtered and dried to obtain an S-4 crude product.
The obtained S-4 crude product was put into ethyl acetate (10 ml), stirred at 70 ° C. for 1 hour, and the precipitate was filtered and dried to obtain S-4 (iodine salt) as a blue crystalline powder.
The obtained S-4 (iodine salt) was dissolved in methanol (5 ml), and a solution in which bis (trifluoromethanesulfonyl) imide lithium (0.5 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in water (1 ml) was added dropwise. Further, 1 ml of water was mixed and stirred at room temperature for 1 hour.
The obtained precipitate was filtered and dried to obtain an exemplary compound (S-4: the above structure, 8.5 g) as a green crystal powder. The obtained exemplary compound (s-4) was subjected to MALDI-MASS mass spectrometry. As a result, M + = 713.39, which was confirmed to be the target compound.

(Synthesis Example 2: Synthesis of Exemplified Compound (S-25))
1-1. Synthesis of synthetic intermediate (S-25A) 2,4-lutidine (4.28 g, manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-bromopropiophenone (9.36 g, manufactured by Tokyo Chemical Industry Co., Ltd.) in acetone (40 ml, Wako Pure Chemical Industries, Ltd.) Mixed and dissolved at room temperature (25 ° C.). Next, the mixture was stirred and reacted for 6 hours under reflux. After cooling the reaction solution, 120 ml of water and potassium carbonate (2.4 g, manufactured by Wako Pure Chemical Industries, Ltd.) were added, and the mixture was heated and stirred at 100 ° C. for 2 hours.
Ethyl acetate (200 ml) was added to the resulting reaction solution, the ethyl acetate layer was separated, dried over magnesium sulfate and concentrated to obtain a synthetic intermediate S-25A crude product. The obtained crude product was purified by column chromatography to obtain a synthetic intermediate S25A (4.3 g).

1-2. Synthesis of Exemplified Compound (S-25) Synthetic simplified form (S-25A, 0.22 g) obtained as described above and N-[(3- (anilinomethylene) -2-chloro-1-cyclohexene -1-yl) methylene] aniline hydrochloride (0.54 g, manufactured by Aldrich) was mixed and dissolved in acetic anhydride (5 ml, manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C.). Next, the reaction solution was stirred and reacted at 100 ° C. for 2 hours. After cooling the reaction solution, it was reprecipitated in 30 ml of water, and the resulting precipitate was filtered and dried to obtain an S-4 crude product (Cl-salt).
The obtained S-4 (Cl-salt) was dissolved in methanol (5 ml), and a solution prepared by dissolving bis (trifluoromethanesulfonyl) imide lithium (0.5 g, manufactured by Tokyo Chemical Industry Co., Ltd.) in 1 ml of water was added dropwise. Further, 1 ml of water was mixed and stirred at room temperature for 1 hour.
The resulting precipitate was filtered and dried to obtain an exemplary compound (S-25: the above structure, 0.12 g) as a green crystalline powder. The obtained exemplary compound (S-25) was subjected to mass spectrometry by MALDI-MASS, and as a result, M + = 819.24 was confirmed to be the target compound.

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 16210.0 parts dissolved in propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 90.0 parts (T-1) Photopolymerizable compound: Kayrad DPHA (manufactured by Nippon Kayaku Co., Ltd. A mixture of pentaerythritol 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)
(W-1) Photopolymerization initiation assistant: 4,4′-bis (diethylamino) benzophenone (manufactured by Ciba Specialty Chemicals)
(X-1) Solvent: Propylene glycol monomethyl ether acetate (X-2) Solvent: Ethyl 3-ethoxypropionate (Y-1) Surfactant: Megafac F781-F (manufactured by Dainippon Ink & Chemicals, Inc.)

Example 1
(Preparation of cyan colored film)
Preparation of colored curable composition (coating liquid) Components in the following composition were mixed to prepare a colored curable composition 1.
<Composition>
-Compound S-1 of the invention ... 6.9 parts by mass-(T-1) ... 103.4 parts by mass-(U-1) ... 212.2 parts by mass (in terms of solid content) : 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, (Y-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 colored curable composition)
The following evaluation was performed about the board | substrate obtained above.
<Evaluation of hue>
About the produced colored film, the ultraviolet absorption visible spectrophotometer (Shimadzu Corporation UV2400-PC) measured the absorption maximum position of the dye in ethanol, the H aggregate absorption maximum position, and the transmittance at 550 nm / 580 nm. Here, the H-aggregate absorption maximum position is an absorption maximum observed on the shorter wavelength side than the absorption maximum position in ethanol of the dye used in the present invention. This shift of the absorption maximum is achieved by blending with the alkali-soluble polymer used in the present invention, and it is predicted that the H aggregate of the dye used in the present invention is formed.
Those having an absorption maximum of H aggregates of 630 nm or less are too short, indicating that a green filter with high color purity cannot be produced in combination with a yellow colorant. Moreover, the transmittance is preferably high in both wavelength regions, and the transmittance ratio represents a short cut on the short wave side, so that the transmittance ratio is preferably as small as possible.

<Evaluation of heat resistance>
About the produced colored film, it heated on 200 degreeC / 30 minute conditions, the absorption spectrum change before and behind a heating was measured with the ultraviolet visible spectrophotometer (Shimadzu Corporation UV2400-PC), and an absorption maximum value (at an absorption maximum position) Abs.Change rate) The change rate was evaluated.
It can be evaluated that heat resistance is so high that this change rate value is low.

  In Example 1 described above, the type of dye was changed as shown in the following table, and the others were performed in the same manner. These results are also shown in the table below.

Example 12
(Production of green colored film)
Preparation of colored curable composition (coating liquid) The components in the following composition were mixed to prepare a colored curable composition.
<Composition>
-Compound S-1 of the invention-6 parts by mass-Yellow colored substance (said (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 so as to fit within the range.
-(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, (Y-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 a maximum at 600 to 700 nm on a 100 mm × 100 mm glass substrate (1737, manufactured by Corning). It apply | coated so that a light absorbency might be 1.5-2.0, it was made to dry for 180 second in 100 degreeC oven, and the colored film was produced on the board | substrate.

Evaluation of colored film by curable colored curable composition The above-described substrate was evaluated for hue and heat resistance. The results are shown below.

  Furthermore, in Example 12, the kind of dye was changed as shown in the following table, and the others were performed in the same manner. These results are also shown in the table below.

As is clear from the above examples, the cyanine dye has an absorption maximum in methanol of 720 nm or more in methanol, and in a specific alkali-soluble polymer, the absorption maximum shifts to around 640 to 650 nm on the short wavelength side, and such It was confirmed that when the absorption maximum gave a spectrum showing a steep rise, it had an optimum hue as a green filter combined with a cyan colorant or a yellow colorant, and could exhibit high heat resistance. This was considered that the dye formed H aggregates in the alkali-soluble polymer.
Further, from comparison between Comparative Example 1 and Example 2 or Example 13, it was found that having a substituent around the methine chain, which is a feature of the cyanine dye, has a great effect on imparting heat resistance.
This is an effective method to improve the weakness of cyanine dyes, which is said to be conventional, and it is an effective measure that can simultaneously optimize the absorption maximum position of H aggregates in order to show a long wave effect. It was done.

Claims (14)

(A) a cyanine dye or squarylium dye having an absorption maximum in methanol of 720 nm or more,
(B) It has an alkali-soluble polymer having a carboxylic acid, sulfonic acid or phosphoric acid value of 150 mgKOH / g or less and (C) a polymerizable compound, and the (A) dye is less in the (B) alkali-soluble polymer. Originally, a colored curable composition characterized by having an absorption maximum at 620 to 670 nm. The transmittance ratio (550 nm / 580 nm) of the transmittance at 550 nm and the transmittance at / 580 nm in the (B) alkali-soluble polymer of the (A) dye is 1.2 to 1.0. The colored curable composition described in 1. Furthermore, the colored curable composition of Claim 1 or 2 containing a photoinitiator. The (A) dye is a compound represented by any one of the following formulas (I), (II), (III), (IV), (VI) and (VII): The colored curable composition of any one of Claims 1.

(In the formula, R _{1 to} R ₅₀ are respectively hydrogen, alkyl group, alkoxy group, hydroxyl group, ether group, thiol group, arylamino group, alkylamino group, thioether group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group. An arylketo group, an alkylketo group, a cyano group, a halogen atom, an aryl group or a heteroaryl group, wherein R _{1 to} R ₅₀ each form an aliphatic or aromatic ring between the condensable sites. Or may have a substituent.
n is an integer of 1 to 3.
X is an oxygen atom, a sulfur atom or CR ₅₁ R ₅₂ , and R ₅₁ and R ₅₂ are each an alkyl group.
M ⁻ is a counter anion of the cyanine dye, and is BF ⁴⁻ , PF ⁶⁻ , SbF ^6−, or an anion represented by the following general formula (V):

(In the formula, R ₅₃ and R ₅₄ are each a perfluoroalkyl group or a perfluoroaryl group.)

(Wherein R _{55 to} R ₇₂ are each hydrogen, alkyl group, alkoxy group, hydroxyl group, ether group, thiol group, arylamino group, alkylamino group, thioether group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group. An arylketo group, an alkylketo group, a cyano group, a halogen, an aryl group, or a heteroaryl group, each of R _{55 to} R ₇₂ forms an aliphatic or aromatic ring between the condensable sites; X may be an oxygen atom, a sulfur atom, or CR ₅₁ R ₅₂ , and R ₅₁ and R ₅₂ are each an alkyl group. Furthermore, the colored curable composition of any one of Claims 1-4 containing the coloring compound (D) different from the said (A) dye. The colored curable composition according to claim 5, wherein the colored compound (D) is a yellow colored compound. (A) a cyanine dye or squarylium dye having an absorption maximum in methanol of 720 nm or more,
(B) having an alkali-soluble polymer having a carboxylic acid, sulfonic acid or phosphoric acid value of 150 mgKOH / g or less and (C) a polymerizable compound, wherein the (A) dye is in the (B) alkali-soluble polymer A colored curable composition characterized by forming H association. The color filter which has a colored layer using the colored curable composition of any one of Claims 1-7. Applying the colored curable composition according to any one of claims 1 to 7 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 comprising the color filter according to claim 8 or the color filter produced by the method for producing a color filter according to claim 9. A solid-state imaging device having a color filter according to claim 8 or a color filter produced by the method for producing a color filter according to claim 9. A compound represented by the following general formula (VIII) or (IX).

(Wherein, R ⁸² to R ⁸⁵ are each an alkyl group, an alkoxycarbonyl group, a cyano group, an aryl group, a heteroaryl group, these groups may have a substituent. Further, R ⁸² two members to the to R ⁸⁵ may form a ring.
M ⁻ is a counter anion of the cyanine dye, and is BF ⁴⁻ , PF ⁶⁻ , SbF ^6−, or an anion represented by the following general formula (V):

(In the formula, R ₅₃ and R ₅₄ are each a perfluoroalkyl group or a perfluoroaryl group.) 13. The compound according to claim 12, wherein R ₈₄ , R ₈₈ , R ₈₅ and R ₉₆ are each an alkyl group, alkoxycarbonyl group, cyano group, aryl group or heteroaryl group, R ₇₃ and R A compound in which ₇₅ are bonded to each other to form an aliphatic ring or an aromatic ring. The following compounds.